CN1288221C - Solvent-free high-strength polyurethane cementing sealing glue and method for making same - Google Patents
Solvent-free high-strength polyurethane cementing sealing glue and method for making same Download PDFInfo
- Publication number
- CN1288221C CN1288221C CN 200410024290 CN200410024290A CN1288221C CN 1288221 C CN1288221 C CN 1288221C CN 200410024290 CN200410024290 CN 200410024290 CN 200410024290 A CN200410024290 A CN 200410024290A CN 1288221 C CN1288221 C CN 1288221C
- Authority
- CN
- China
- Prior art keywords
- isocyanic ester
- condition
- stir
- under
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Sealing Material Composition (AREA)
Abstract
The present invention relates to a solvent-free high-strength polyurethane bonding sealing gum and a preparation method thereof, which belongs to the field of adhesive. The polyurethane bonding sealing gum comprises the components of the following portions by mass: 15 to 40 portions by mass of hydroxy terminated polyether, 3 to 10 portions by mass of isocyanate, 10 to 8 portions by mass of plasticizer, 6 to 25 portions by mass of inorganic filler, 3 to 1523 portions by mass of organic filler, 0.01 to 0.3 portion by mass of catalyst and 0.01 to 0.2 portion by mass of antioxidant. Due to the fact that the component formula of the polyurethane bonding sealing gum has no solvent component, the polyurethane bonding sealing gum has the advantages of no harm to environment, production and the health of users, good toughness, high solid content, high tensile strength and good anti-ultraviolet stability. The polyurethane bonding sealing gum can be widely used for the fields of the construction of buildings, squares, highways and airports, the manufacturing industry of automobiles, ships, containers and machinery, and the technology of electrons, electric power, aviation/spaceflight and low temperature, etc.
Description
Technical field
The invention belongs to adhesive field, relate in particular to a kind of tackiness agent/seal gum based on urethane or this kind polymer derivant.
Background technology
Seal gum (Sealant) is the material that is used for filling space (cavity, joint or seam etc.).But it is the unsetting material of a kind of mobile or squeeze note in use, can seal seam by pointing, can rely on drying, temperature variation, solvent evaporates or chemically crosslinked, with the base material stable adhesion, and finalize the design gradually become that plasticity is solid-state, visco-elasticity or elaxtic seal.
Over nearly 30 years, the application of seal gum in industry such as building, building, automobile, boats and ships, electric, communication, space flight and civil area more and more widely.
That the kind of indefiniteness seal gum mainly contains is silicone based, polyurethanes, thiorubber class, acrylics, styrene-butadiene rubber(SBR) class, butyl type rubber, pitch class and oiliness caulk compound class, wherein better performances, use and mainly contain silicone based, polyurethanes and thiorubber class seal gum more widely.
Polyurethane sealant (Polyurethane Sealant) generally is divided into single component and two kinds of base types of two-pack, and single component is a moisture-curable, and two-pack is a reaction-curable.The single component sealant easy construction, but solidify slower; The two-pack seal gum has characteristics such as quick solidifying, performance are good, but needs preparation when using, and technology is comparatively complicated.
Polyurethane sealant is mainly used in industries such as civil construction, communications and transportation, in Japan, about 75～80% polyurethane sealant is because building trades such as buildings, square, highway, airport constructions, about 15% be used for machine industries such as automobile, boats and ships, freight container, about 5% be used for other industries such as electronics, electric power, aviation/space flight, low temperature technique.
China's exploitation polyurethane sealant starts from the seventies in 20th century, and the polyurethane sealant of early stage development is the two-pack tar oil type.The research and development of single component sealant is slower, to early 1990s, tackles key problems by " the Seventh Five-Year Plan ", develop one-component polyurethane sealant, the back begins the industrialized mass production one-component polyurethane sealant by technology introduction, and its product is mainly used in building trade.
Because polyurethane sealant has better physical performance and endurance quality, strong to base material adaptability, the streamline operration and the curing speed that can have the quick assembling line of suitable automobile, the assembling and the sealing of windshield have been widely used in the country of automotive industry prosperity, the sealing at crash bar, headlight, back door etc. is held concurrently bonding, makes these component joints have antirust, waterproof and dustproof, antidetonation and enhancement.
At present, that can produce this class high quality single component polyurethane adhesive agent/seal gum product in the world has only minority developed country, as the EMS-TOGO company of the BOSTIK company of the SUNSTAR company of the ESSEX company of the U.S., 3M company, Japan, ponding chemical company, Yokohama Rubber company, Germany, Switzerland and SIKA company etc.
Open day is on December 25th, 2002, publication number is to disclose a kind of " preparation of wet-solidifying single-component polyurethane adhesive and application thereof " in the Chinese patent application of CN 1386815A, it is with vulcabond and polyether glycol prepared in reaction, and each raw material consumption is as follows by weight percentage:
Polyether Glycols 27.6～58.0%, polyether-tribasic alcohol 0～13.0%, 4,4 '-diphenylmethanediisocyanate 31.4～55.0%, solvent 0～20%.
The day for announcing is on March 29th, 2000, and notification number is to disclose a kind of " polyurethane binder/sealant composition, its precursor and preparation method " in the Chinese patent of CN 1248606C, by weight, contains in its component:
100 parts of binder/sealant precursors;
Block agent 0.04-1.78 part;
Inert filler 32-76 part;
Inert plasticizer 24-134 part;
Other additives 1.2-3.6 part;
Inert solvent is less than 9 parts greater than 0 part.
Above-mentioned about polyurethane binder/sealant patent application or patent in the disclosed component, all contain solvent.
Solvent as used herein has benzene,toluene,xylene etc. usually, and (referring to " seal gum-technical formula is used " that publish September calendar year 2001 Chemical Industry Press Materials Science and Engineering publishing centre, Cao Yun compiles, P.19).
Because existing polyurethane binder/sealant has all used noxious solvent more or less in prescription or production process, make it have certain environmental pollution and environmental issue, the producer and user healthy brought certain infringement.
In addition, as automobile single-component high-strength polyurethane joint sealant, the present solid content of similar products at home and abroad (wherein 4% is noxious solvent such as dimethylbenzene) about 96%, tensile strength about about 6MPa, is limited to its range of application in the automobile production industry greatly.
Summary of the invention
Technical problem to be solved by this invention provides a kind of solvent-free, solids content is high, snappiness good, tensile strength is high, ultraviolet stability is good solvent-free high-strength polyurethane joint sealant.
The present invention also provides the preparation method of above-mentioned polyurethane adhesive/seal gum.
Technical scheme of the present invention is: a kind of solvent-free high-strength polyurethane joint sealant is provided, it is characterized in that the mass fraction ratio of polyurethane adhesive/seal gum component is:
End hydroxy polyether 15～40
Isocyanic ester 3～10
Softening agent 10～38
Mineral filler 6～25
Organic filler 3～15
Catalyzer 0.01～0.3
Oxidation inhibitor 0.01～0.2
Wherein,
Described end hydroxy polyether is that molecular-weight average is that 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether, molecular-weight average are that 6000～8000 hydroxy-terminated polytetrahydrofuran ether, molecular-weight average are 5500～6500 the polyoxytrimethylene-castor oil polyhydric alcohol copolyether or the polytetrahydrofuran-propylene oxide copolyether of molecular-weight average 2000～4000;
Described isocyanic ester is a tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or two kinds mixture wherein;
Described softening agent is dibutyl phthalate, dioctyl phthalate (DOP), Dinonylphthalate or Di Iso Decyl Phthalate;
Described mineral filler is Shawinigan black, titanium dioxide, lime carbonate, talcum powder, 4A molecular sieve, Tai-Ace S 150, magnesium oxide, organobentonite or thermal silica;
Described organic filler is resol, acrylic ester oligomer, vinylbenzene oligopolymer, Resins, epoxy, PVC paste resin or terpine resin;
Described catalyzer is stannous octoate, dibutyl tin laurate, triethylene diamine, N-methylmorpholine or trolamine;
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol, tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester or 4,4 '-two uncle's octyl diphenylamines.
Further, above-mentioned tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, 1, hexamethylene-diisocyanate can use separately, also wherein two kinds of mixing are used, mix when using, the blending ratio of its two kinds of mixtures is 1: 1～1.5.
The present invention also provides a kind of preparation method of above-mentioned solvent-free high-strength polyurethane joint sealant, it is characterized in that preparation technology is followed successively by:
(1) end hydroxy polyether of getting required umber by prescription joins in the stirred autoclave, is warming up to 80～100 ℃ in 30～60min, vacuum tightness be stir under 0.09 ± 0.005MPa condition, vacuum outgas 1～2h, be cooled to 60～80 ℃;
(2) organic filler and the isocyanic ester of the required umber of adding are warming up to 80～100 ℃ in 30～60min, react 2～3h under the inflated with nitrogen protective condition;
(3) softening agent of the required umber of adding is to stir 1～2h under 0.09 ± 0.005MPa condition in 80～100 ℃ of temperature and vacuum tightness;
(4) mineral filler of the required umber of adding, even back to be mixed is to stir 1～2h under 0.09 ± 0.005MPa condition in vacuum tightness, is cooled to 30～40 ℃;
(5) catalyzer and the oxidation inhibitor of the required umber of adding continue reaction 1～2h;
(6) viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, stop to stir, continue to vacuumize 10～15min;
(7) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then;
(8) through check, divide packing and make finished product.
When above-mentioned isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing.
The present invention also provides the another kind of preparation method of above-mentioned solvent-free high-strength polyurethane joint sealant, it is characterized in that preparation technology is followed successively by:
(1) end hydroxy polyether and the softening agent of getting required umber by prescription joins in the stirred autoclave, is warming up to 100～120 ℃ in 30～60min, is to stir under 0.09 ± 0.005MPa condition in vacuum tightness, vacuum outgas 1～2h;
(2) mineral filler of the required umber of adding, continuing in vacuum tightness is to stir 1～2h under 0.09 ± 0.005MPa condition, is cooled to 60～80 ℃;
(3) organic filler and the isocyanic ester of the required umber of adding are warming up to 80～100 ℃ in 30～60min, are to react 2～3h under 0.09 ± 0.005MPa condition in vacuum tightness, are cooled to 60～80 ℃;
(4) catalyzer and the oxidation inhibitor of the required umber of adding under the inflated with nitrogen protective condition continue stirring reaction 1～2h;
(5) viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, be cooled to 20～30 ℃, stop to stir, vacuumize 10～15min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
When described isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing.
Compared with the prior art, advantage of the present invention is:
1. no any solvent composition in its component prescription does not have harm to environment and production, user's health;
2. solid content is greater than 99.5%, and tensile strength obviously is better than present similar products at home and abroad (solid content of similar products at home and abroad is about 96% at present, and tensile strength is about 6MPa) greater than 10MPa;
3. by add oxidation inhibitor in prescription, make the ultraviolet stability of product of the present invention be improved, prolong work-ing life greatly.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is that molecular-weight average is 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether;
Organic filler is a resol;
Isocyanic ester is a tolylene diisocyanate;
Softening agent is a dibutyl phthalate;
Mineral filler is Shawinigan black or thermal silica;
Catalyzer is a stannous octoate;
Oxidation inhibitor is 2,6 ditertiary butyl p cresol.
Preparation technology:
(1) get the 15kg end hydroxy polyether and join in the stirred autoclave, warming-in-water to 80 ℃ in 30min, vacuum tightness be stir under the 0.095MPa condition, vacuum outgas 1h, be cooled to 60 ℃;
(2) add organic filler and the 3kg isocyanic ester of 3kg, warming-in-water to 80 ℃ in 30min is reacted 2h under the inflated with nitrogen protective condition;
(3) softening agent of adding 10kg is to stir 1h under the 0.095MPa condition in 80 ℃ of temperature and vacuum tightness;
(4) mineral filler of adding 6kg, even back to be mixed is to stir 1h under the 0.095MPa condition in vacuum tightness, is cooled to 30 ℃;
(5) add the catalyzer of 0.01kg and the oxidation inhibitor of 0.01kg, continue reaction 1h;
(6) viscosity of testing product reaches 11 * 10
5During mPas, stop to stir, continue to vacuumize 10min;
(7) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then;
(8) through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index and as shown in the table with the index value contrast of external like product:
| Performance | SIKAFLEX | TRESTAT | BETASAD | AM-140 | Product of the present invention | |
| 255 | 255FC | 8590 | 551 | |||
| Solids content (%) | 95 | 95 | 95 | 95 | 95 | 100 |
| Density (g/ml) | 1.29 | 1.29 | 1.16 | 1.3 | 1.1 | 1.21 |
| The not sticking time (min) | 30 | 15 | 30 | 37 | 40-50 | 30 |
| Curing speed (mm/d) | 8.0 | 5.0 | 4.0 | 4.0 | 4.0 | |
| Hardness (Shao Shi A °) | 60 | 60 | 50 | 49 | 55 | 45 |
| Stretching bonding strength (MPa) | 8.0 | 5.0 | 5.2 | 4.2 | 6.0 | 13 |
| Elongation (%) | 400 | 400 | 450 | 500 | 500 | 550 |
| Shearing resistance (MPa) | 5.0 | 5.0 | 5.5 | 4.0 | 4.5 | 6.0 |
| Tear strength (N/mm) | 9.0 | 12.0 | 6.4 | 17.4 | 15 | 20 |
As seen, indexs such as the solids content of product of the present invention, stretching bonding strength, shearing resistance and tear strength all are better than external like product.
The mensuration of above-mentioned parameter is tested by the method for stipulating in the following standard:
The mensuration of GB/T528-1999 vulcanized rubber or thermoplastic elastomer tensile property;
The mensuration of GB/T529-1999 vulcanized rubber or thermoplastic elastomer tear strength;
The pocket sclerometer penetration hardness of GB/T531-1999 rubber test method;
GB/T6680-1986 fluid chemical product sampling general rule;
Q/HTM-001-2003 monocomponent moisture cure urethanes adhesive/seal gum.
In the foregoing description inflated with nitrogen protection purpose be for guarantee to be reflected at the air state of isolation under carry out, do not have strict demand so fill nitrogen pressure.
Embodiment 2:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is that molecular-weight average is 6000～8000 hydroxy-terminated polytetrahydrofuran ether;
Organic filler is an acrylic ester oligomer;
Isocyanic ester is 1, the 5-naphthalene diisocyanate;
Softening agent is a dioctyl phthalate (DOP);
Mineral filler is titanium dioxide or lime carbonate;
Catalyzer is a dibutyl tin laurate;
Oxidation inhibitor is tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester.
Preparation technology:
(1) get the 40kg end hydroxy polyether and the 38kg softening agent joins in the stirred autoclave, warming-in-water to 120 ℃ in 60min is to stir under the 0.09MPa condition in vacuum tightness, vacuum outgas 2h;
(2) add the 25kg mineral filler, continuing in vacuum tightness is to stir 2h under the 0.09MPa condition, is cooled to 80 ℃;
(3) add 15kg organic filler and 10kg isocyanic ester, warming-in-water to 100 ℃ in 60min is to react 3h under the 0.09MPa condition in vacuum tightness, is cooled to 80 ℃;
(4) under the inflated with nitrogen protective condition, add 0.3kg catalyzer and 0.2kg oxidation inhibitor, continue stirring reaction 2h;
(5) viscosity of testing product reaches 13 * 10
5During mPas, be cooled to 30 ℃, stop to stir, vacuumize 15min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Solids content (%) | 99.98 |
| Density (g/ml) | 1.19 |
| The not sticking time (min) | 40 |
| Curing speed (mm/d) | 4.02 |
| Hardness (Shao Shi A °) | 50 |
| Stretching bonding strength (MPa) | 12.8 |
| Elongation (%) | 548 |
| Shearing resistance (MPa) | 6.1 |
| Tear strength (N/mm) | 20.3 |
All the other are with embodiment 1.
Embodiment 3:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is that molecular-weight average is polyoxytrimethylene-castor oil polyhydric alcohol copolyether of 5500～6500;
Organic filler is the vinylbenzene oligopolymer;
Isocyanic ester is a diphenylmethanediisocyanate;
Softening agent is a Dinonylphthalate;
Mineral filler is talcum powder or Tai-Ace S 150;
Catalyzer is a triethylene diamine;
Oxidation inhibitor is 4,4 '-two uncle's octyl diphenylamines.
Preparation technology:
(1) get the 27.5kg end hydroxy polyether and join in the stirred autoclave, warming-in-water to 100 ℃ in 45min, vacuum tightness be stir under the 0.085MPa condition, vacuum outgas 2h, be cooled to 80 ℃;
(2) add 9kg organic filler and 7kg isocyanic ester, warming-in-water to 100 ℃ in 45min is reacted 3h under the inflated with nitrogen protective condition;
(3) adding the 24kg softening agent, is to stir 2h under the 0.085MPa condition in 100 ℃ of temperature and vacuum tightness;
(4) add the 15.5kg mineral filler, even back to be mixed is to stir 2h under the 0.085MPa condition in vacuum tightness, is cooled to 40 ℃;
(5) add 0.155kg catalyzer and 0.105kg oxidation inhibitor, continue reaction 2h;
(6) viscosity of testing product reaches 13 * 10
5During mPas, stop to stir, continue to vacuumize 15min;
(7) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then;
(8) through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Solids content (%) | 100 |
| Density (g/ml) | 1.19 |
| The not sticking time (min) | 35 |
| Curing speed (mm/d) | 4.02 |
| Hardness (Shao Shi A °) | 50 |
| Stretching bonding strength (MPa) | 12.8 |
| Elongation (%) | 548 |
| Shearing resistance (MPa) | 6.05 |
| Tear strength (N/mm) | 21 |
All the other are with embodiment 1.
Embodiment 4:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is the polytetrahydrofuran-propylene oxide copolyether of molecular-weight average 2000～4000;
Organic filler is a Resins, epoxy;
Isocyanic ester is an isophorone diisocyanate;
Softening agent is a Di Iso Decyl Phthalate;
Mineral filler is the 4A molecular sieve;
Catalyzer is a N-methylmorpholine;
Oxidation inhibitor is 2,6 ditertiary butyl p cresol.
Preparation technology:
(1) getting the 21.3kg end hydroxy polyether and the 17kg softening agent joins in the stirred autoclave, be warming up to 100 ℃ in 30min, is to stir under the 0.09MPa condition in vacuum tightness, vacuum outgas 1h;
(2) add the 10.8kg mineral filler, continuing in vacuum tightness is to stir 1h under the 0.09MPa condition, is cooled to 60 ℃;
(3) adding 6kg organic filler and 5kg isocyanic ester, be warming up to 80 ℃ in 30min, is to react 2h under the 0.09MPa condition in vacuum tightness, is cooled to 60 ℃;
(4) under the inflated with nitrogen protective condition, add 0.0725kg catalyzer and 0.0575kg oxidation inhibitor, continue stirring reaction 1h;
(5) viscosity of testing product reaches 11 * 10
5During mPas, be cooled to 20 ℃, stop to stir, vacuumize 10min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make mouthful product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Solids content (%) | 99.9 |
| Density (g/ml) | 1.19 |
| The not sticking time (min) | 27 |
| Curing speed (mm/d) | 4.02 |
| Hardness (Shao Shi A °) | 52 |
| Stretching bonding strength (MPa) | 13.7 |
| Elongation (%) | 552 |
| Shearing resistance (MPa) | 6.03 |
| Tear strength (N/mm) | 20.2 |
All the other are with embodiment 2.
In the various embodiments described above, when the isocyanic ester that is adopted is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing (following each embodiment is also identical).
Embodiment 5:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is that molecular-weight average is 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether;
Organic filler is that PVC sticks with paste resin;
Isocyanic ester is a hexamethylene diisocyanate;
Softening agent is a dioctyl phthalate (DOP);
Mineral filler is magnesium oxide or organobentonite;
Catalyzer is a trolamine;
Oxidation inhibitor is tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester.
Preparation technology:
(1) get the 33.75kg end hydroxy polyether and join in the stirred autoclave, warming-in-water to 95 ℃ in 50min, vacuum tightness be stir under the 0.093MPa condition, vacuum outgas 1.75h, be cooled to 75 ℃;
(2) add the organic filler and the isocyanic ester of required umber, warming-in-water to 76 ℃ in 50min is reacted 2.75h under the inflated with nitrogen protective condition;
(3) softening agent of the required umber of adding is to stir 1.75h under the 0.093MPa condition in 95 ℃ of temperature and vacuum tightness;
(4) mineral filler of the required umber of adding, even back to be mixed is to stir 1.75h under the 0.093MPa condition in vacuum tightness, is cooled to 37 ℃;
(5) catalyzer and the oxidation inhibitor of the required umber of adding continue reaction 1.75h;
(6) viscosity of testing product reaches 12.5 * 10
5During mPas, stop to stir, continue to vacuumize 13.5min;
(7) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then;
(8) through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as shown in the table:
| Solids content (%) | 100 |
| Density (g/ml) | 1.21 |
| The not sticking time (min) | 27 |
| Curing speed (mm/d) | 4.02 |
| Hardness (Shao Shi A °) | 56 |
| Stretching bonding strength (MPa) | 13.2 |
| Elongation (%) | 550 |
| Shearing resistance (MPa) | 6.05 |
| Tear strength (N/mm) | 21 |
All the other are with embodiment 1.
Embodiment 6:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is that molecular-weight average is 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether;
Organic filler is a terpine resin;
Isocyanic ester is a diphenylmethanediisocyanate;
Softening agent is a dioctyl phthalate (DOP);
Mineral filler is organobentonite or thermal silica;
Catalyzer is a N-methylmorpholine;
Oxidation inhibitor is 2,6 ditertiary butyl p cresol.
Preparation technology:
(1) getting the 34kg end hydroxy polyether and the 31kg softening agent joins in the stirred autoclave, be warming up to 115 ℃ in 60min, is to stir under the 0.095MPa condition in vacuum tightness, vacuum outgas 1.5h;
(2) add the 20.3kg mineral filler, continuing in vacuum tightness is to stir 1.5h under the 0.095MPa condition, is cooled to 70 ℃;
(3) adding 12kg organic filler and 8.5kg isocyanic ester, be warming up to 90 ℃ in 60min, is to react 1.5h under the 0.095MPa condition in vacuum tightness, is cooled to 70 ℃;
(4) under the inflated with nitrogen protective condition, add 0.228kg catalyzer and 0.153kg oxidation inhibitor, continue stirring reaction 1.6h;
(5) viscosity of testing product reaches 12.5 * 10
5During mPas, be cooled to 25 ℃, stop to stir, vacuumize 12.5min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.。
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Solids content (%) | 99.97 |
| Density (g/ml) | 1.2 |
| The not sticking time (min) | 28 |
| Curing speed (mm/d) | 4.0 |
| Hardness (Shao Shi A °) | 53 |
| Stretching bonding strength (MPa) | 13.5 |
| Elongation (%) | 553 |
| Shearing resistance (MPa) | 6.02 |
| Tear strength (N/mm) | 20.4 |
All the other are with embodiment 2.
Embodiment 7:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is that molecular-weight average is polyoxytrimethylene-castor oil polyhydric alcohol copolyether of 5500～6500;
Organic filler is that PVC sticks with paste resin;
Isocyanic ester is a hexamethylene diisocyanate, or two kinds mixture wherein;
Softening agent is a Dinonylphthalate;
Mineral filler is a thermal silica;
Catalyzer is a triethylene diamine;
Oxidation inhibitor is tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester.
Preparation technology:
(1) get the 35kg end hydroxy polyether and join in the stirred autoclave, warming-in-water to 85 ℃ in 50min, vacuum tightness be stir under the 0.085MPa condition, vacuum outgas 1.25h, be cooled to 65 ℃;
(2) add 7kg organic filler and 6kg isocyanic ester, warming-in-water to 88 ℃ in 40min is reacted 2.3h under the inflated with nitrogen protective condition;
(3) adding the 35kg softening agent, is to stir 1.25h under the 0.085MPa condition in 85 ℃ of temperature and vacuum tightness;
(4) add the 18kg mineral filler, even back to be mixed is to stir 1.5h under the 0.085MPa condition in vacuum tightness, is cooled to 32.5 ℃:
(5) add 0.25kg catalyzer and 0.16kg oxidation inhibitor, continue reaction 1.2h;
(6) viscosity of testing product reaches 11.5 * 10
5During mPas, stop to stir, continue to vacuumize 11.5min;
(7) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then;
(8) through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Solids content (%) | 100 |
| Density (g/ml) | 1.2 |
| The not sticking time (min) | 40 |
| Curing speed (mm/d) | 4.0 |
| Hardness (Shao Shi A °) | 50.3 |
| Stretching bonding strength (MPa) | 14 |
| Elongation (%) | 547 |
| Shearing resistance (MPa) | 6.03 |
| Tear strength (N/mm) | 21 |
All the other are with embodiment 1.
Embodiment 8:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is the polytetrahydrofuran-propylene oxide copolyether of molecular-weight average 2000～4000;
Organic filler is a terpine resin;
Isocyanic ester is an isophorone diisocyanate;
Plasticizer phthalic acid ester in two ninth of the ten Heavenly Stems;
Mineral filler is the 4A molecular sieve;
Catalyzer is a trolamine;
Oxidation inhibitor is 2,6 ditertiary butyl p cresol.
Preparation technology:
(1) getting the 20kg end hydroxy polyether and the 15kg softening agent joins in the stirred autoclave, be warming up to 110 ℃ in 45min, is to stir under 0.09 ± 0.005MPa condition in vacuum tightness, vacuum outgas 1～2h;
(2) add the 9kg mineral filler, continuing in vacuum tightness is to stir 1.5h under the 0.09MPa condition, is cooled to 65 ℃;
(3) adding 5kg organic filler and 4.5kg isocyanic ester, be warming up to 95 ℃ in 40min, is to react 1.3h under the 0.09MPa condition in vacuum tightness, is cooled to 75 ℃;
(4) under the inflated with nitrogen protective condition, add 0.22kg catalyzer and 0.02kg oxidation inhibitor, continue stirring reaction 1.5h;
(5) viscosity of testing product reaches 11.5 * 10
5During mPas, be cooled to 30 ℃, stop to stir, vacuumize 1min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Solids content (%) | 100 |
| Density (g/ml) | 1.2 |
| The not sticking time (min) | 20～40 |
| Curing speed (mm/d) | 4.0 |
| Hardness (Shao Shi A °) | 45-55 |
| Stretching bonding strength (MPa) | 13 |
| Elongation (%) | 550 |
| Shearing resistance (MPa) | 6.0 |
| Tear strength (N/mm) | 20 |
All the other are with embodiment 2.
Embodiment 9:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is the polytetrahydrofuran-propylene oxide copolyether of molecular-weight average 2000～4000;
Organic filler is a terpine resin;
Isocyanic ester is the first diphenylmethanediisocyanate;
Softening agent is a dioctyl phthalate (DOP);
Mineral filler is Tai-Ace S 150 or magnesium oxide;
Catalyzer is a stannous octoate, dibutyl tin laurate, triethylene diamine, N-methylmorpholine, trolamine;
Oxidation inhibitor is 4,4 '-two uncle's octyl diphenylamines.
Preparation technology:
(1) get the 30kg end hydroxy polyether and join in the stirred autoclave, warming-in-water to 88 ℃ in 40min, vacuum tightness be stir under the 0.095MPa condition, vacuum outgas 2h, be cooled to 60 ℃;
(2) add 9.5kg organic filler and 11kg isocyanic ester, warming-in-water to 100 ℃ in 40min is reacted 2h under the inflated with nitrogen protective condition;
(3) adding the 32kg softening agent, is to stir 2h under the 0.095MPa condition in 100 ℃ of temperature and vacuum tightness;
(4) add the 22.5kg mineral filler, even back to be mixed is to stir 2h under the 0.095MPa condition in vacuum tightness, is cooled to 30 ℃;
(5) add 0.23kg catalyzer and 0.16kg oxidation inhibitor, continue reaction 1.6h;
(6) viscosity of testing product reaches 12.7 * 10
5During mPas, stop to stir, continue to vacuumize 14min;
(7) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then;
(8) through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as shown in the table:
| Solids content (%) | 100 |
| Density (g/ml) | 1.23 |
| The not sticking time (min) | 36 |
| Curing speed (mm/d) | 4.0 |
| Hardness (Shao Shi A °) | 55 |
| Stretching bonding strength (MPa) | 13.6 |
| Elongation (%) | 549.25 |
| Shearing resistance (MPa) | 6.0 |
| Tear strength (N/mm) | 20 |
All the other are with embodiment 1.
Embodiment 10:
Press following prescription and the solvent-free high-strength polyurethane joint sealant of prepared:
Prescription:
End hydroxy polyether is that molecular-weight average is 6000～8000 hydroxy-terminated polytetrahydrofuran ether;
Organic filler is that PVC sticks with paste resin;
Isocyanic ester is an isophorone diisocyanate;
Softening agent is a dibutyl phthalate;
Mineral filler is the 4A molecular sieve;
Catalyzer is a dibutyl tin laurate;
Oxidation inhibitor is 2,6 ditertiary butyl p cresol.
Preparation technology:
(1) getting the 32kg end hydroxy polyether and the 28kg softening agent joins in the stirred autoclave, be warming up to 117 ℃ in 50min, is to stir under the 0.085MPa condition in vacuum tightness, vacuum outgas 2h;
(2) add the 18.5kg mineral filler, continuing in vacuum tightness is to stir 1.8h under the 0.085MPa condition, is cooled to 65 ℃;
(3) adding 8.5kg organic filler and 8.2kg isocyanic ester, be warming up to 95 ℃ in 50min, is to react 2.6h under the 0.085MPa condition in vacuum tightness, is cooled to 65.5 ℃;
(4) under the inflated with nitrogen protective condition, add 0.18kg catalyzer and 0.125kg oxidation inhibitor, continue stirring reaction 1.6h;
(5) viscosity of testing product reaches 12.8 * 10
5During mPas, be cooled to 30 ℃, stop to stir, vacuumize 15min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the solvent-free high-strength polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Solids content (%) | 99.99 |
| Density (g/ml) | 1.22 |
| The not sticking time (min) | 30 |
| Curing speed (mm/d) | 4.03 |
| Hardness (Shao Shi A °) | 53.9 |
| Stretching bonding strength (MPa) | 13.02 |
| Elongation (%) | 550 |
| Shearing resistance (MPa) | 6.1 |
| Tear strength (N/mm) | 20.2 |
All the other are with embodiment 2.
Embodiment 11:
The isocyanic ester that is adopted is 1.5kg tolylene diisocyanate and 1.5kg 1, the 5-naphthalene diisocyanate;
Mineral filler is 5kg Shawinigan black, 5kg titanium dioxide and 5kg lime carbonate;
All the other are with embodiment 1.
Embodiment 12:
The isocyanic ester that is adopted is 5kg 1,5-naphthalene diisocyanate and 5kg diphenylmethanediisocyanate;
Mineral filler is 20kg talcum powder, 5kg magnesium oxide and 25kg organobentonite;
All the other are with embodiment 2.
Embodiment 13:
The isocyanic ester that is adopted is 3kg tolylene diisocyanate and 4.5kg 1, the 5-naphthalene diisocyanate;
Mineral filler is 10kg titanium dioxide, 14kg lime carbonate and 26kg talcum powder;
All the other are with embodiment 3.
Embodiment 14:
The isocyanic ester that is adopted is 3.5kg isophorone diisocyanate and 4.5kg hexamethylene diisocyanate;
Mineral filler is 20kg talcum powder, 4kg4A molecular sieve and 16kg Tai-Ace S 150;
All the other are with embodiment 4.
Embodiment 15:
The isocyanic ester that is adopted is 2kg tolylene diisocyanate and 2.5kg diphenylmethanediisocyanate;
Mineral filler is 6kg Tai-Ace S 150,8kg magnesium oxide and 3.5kg organobentonite;
All the other are with embodiment 5.
Embodiment 16:
The isocyanic ester that is adopted is 4kg 1,5-naphthalene diisocyanate and 5.2kg hexamethylene diisocyanate;
Mineral filler is 10kg thermal silica, 11kg talcum powder, 2kg 4A molecular sieve and 15kg organobentonite;
All the other are with embodiment 6.
Embodiment 17:
The isocyanic ester that is adopted is 3kg tolylene diisocyanate and 4.4kg isophorone diisocyanate;
Mineral filler is 20kg Shawinigan black, 22kg lime carbonate, 7kg talcum powder, 2kg4A molecular sieve and 2kg magnesium oxide;
All the other are with embodiment 7.
Embodiment 18:
The isocyanic ester that is adopted is 3.5kg diphenylmethanediisocyanate and 4.5kg1, hexamethylene-diisocyanate;
Mineral filler is 11kg Shawinigan black, 10kg titanium dioxide, 7kg talcum powder, 5kg4A molecular sieve and 8kg organobentonite;
All the other are with embodiment 8.
The present invention can be widely used in fields such as buildings, square, highway, airport construction, automobile, boats and ships, freight container, machine industry, electronics, electric power, aviation/space flight, low temperature technique.
Claims (4)
1. the preparation method of a solvent-free high-strength polyurethane joint sealant is characterized in that
(1) the mass fraction ratio of polyurethane adhesive/seal gum component is:
End hydroxy polyether 15～40
Isocyanic ester 3～10
Softening agent 10～38
Mineral filler 6～25
Organic filler 3～15
Catalyzer 0.01～0.3
Oxidation inhibitor 0.01～0.2
Wherein,
Described end hydroxy polyether is that molecular-weight average is that 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether, molecular-weight average are that 6000～8000 hydroxy-terminated polytetrahydrofuran ether, molecular-weight average are 5500～6500 the polyoxytrimethylene-castor oil polyhydric alcohol copolyether or the polytetrahydrofuran-propylene oxide copolyether of molecular-weight average 2000～4000;
Described isocyanic ester is a tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or two kinds mixture wherein;
Described softening agent is dibutyl phthalate, dioctyl phthalate (DOP), Dinonylphthalate or Di Iso Decyl Phthalate;
Described mineral filler is Shawinigan black, titanium dioxide, lime carbonate, talcum powder, 4A molecular sieve, Tai-Ace S 150, magnesium oxide, organobentonite or thermal silica;
Described organic filler is resol, acrylic ester oligomer, vinylbenzene oligopolymer, Resins, epoxy, PVC paste resin or terpine resin;
Described catalyzer is stannous octoate, dibutyl tin laurate, triethylene diamine, N-methylmorpholine or trolamine;
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol, tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester or 4,4 '-two uncle's octyl diphenylamines;
(2) its preparation technology is followed successively by:
1. the end hydroxy polyether of getting required umber by prescription joins in the stirred autoclave, is warming up to 80～100 ℃ in 30～60min, vacuum tightness be stir under 0.09 ± 0.005MPa condition, vacuum outgas 1～2h, be cooled to 60～80 ℃;
2. the organic filler and the isocyanic ester that add required umber are warming up to 80～100 ℃ in 30～60min, react 2～3h under the inflated with nitrogen protective condition;
3. the softening agent that adds required umber is to stir 1～2h under 0.09 ± 0.005MPa condition in 80～100 ℃ of temperature and vacuum tightness;
4. the mineral filler that adds required umber, even back to be mixed is to stir 1～2h under 0.09 ± 0.005MPa condition in vacuum tightness, is cooled to 30～40 ℃;
5. the catalyzer and the oxidation inhibitor that add required umber continue reaction 1～2h;
6. the viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, stop to stir, continue to vacuumize 10～15min;
7. inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then;
8. through check, divide packing and make finished product.
2. according to the preparation method of the described solvent-free high-strength polyurethane joint sealant of claim 1, when it is characterized in that described isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing.
3. the preparation method of a solvent-free high-strength polyurethane joint sealant is characterized in that
(1) the mass fraction ratio of polyurethane adhesive/seal gum component is:
End hydroxy polyether 15～40
Isocyanic ester 3～10
Softening agent 10～38
Mineral filler 6～25
Organic filler 3～15
Catalyzer 0.01～0.3
Oxidation inhibitor 0.01～0.2
Wherein,
Described end hydroxy polyether is that molecular-weight average is that 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether, molecular-weight average are that 6000～8000 hydroxy-terminated polytetrahydrofuran ether, molecular-weight average are 5500～6500 the polyoxytrimethylene-castor oil polyhydric alcohol copolyether or the polytetrahydrofuran-propylene oxide copolyether of molecular-weight average 2000～4000;
Described isocyanic ester is a tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or two kinds mixture wherein;
Described softening agent is dibutyl phthalate, dioctyl phthalate (DOP), Dinonylphthalate or Di Iso Decyl Phthalate;
Described mineral filler is Shawinigan black, titanium dioxide, lime carbonate, talcum powder, 4A molecular sieve, Tai-Ace S 150, magnesium oxide, organobentonite or thermal silica;
Described organic filler is resol, acrylic ester oligomer, vinylbenzene oligopolymer, Resins, epoxy, PVC paste resin or terpine resin;
Described catalyzer is stannous octoate, dibutyl tin laurate, triethylene diamine, N-methylmorpholine or trolamine;
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol, tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester or 4,4 '-two uncle's octyl diphenylamines;
(2) its preparation technology is followed successively by:
1. end hydroxy polyether and the softening agent of getting required umber by prescription joins in the stirred autoclave, is warming up to 100～120 ℃ in 30～60min, is to stir under 0.09 ± 0.005MPa condition in vacuum tightness, vacuum outgas 1～2h;
2. the mineral filler that adds required umber, continuing in vacuum tightness is to stir 1～2h under 0.09 ± 0.005MPa condition, is cooled to 60～80 ℃;
3. the organic filler and the isocyanic ester that add required umber are warming up to 80～100 ℃ in 30～60min, be to react 2～3h under 0.09 ± 0.005MPa condition in vacuum tightness, are cooled to 60～80 ℃;
4. under the inflated with nitrogen protective condition, add the catalyzer and the oxidation inhibitor of required umber, continue stirring reaction 1～2h;
5. the viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, be cooled to 20～30 ℃, stop to stir, vacuumize 10～15min;
6. inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
4. according to the preparation method of the described solvent-free high-strength polyurethane joint sealant of claim 3, when it is characterized in that described isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410024290 CN1288221C (en) | 2004-06-24 | 2004-06-24 | Solvent-free high-strength polyurethane cementing sealing glue and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410024290 CN1288221C (en) | 2004-06-24 | 2004-06-24 | Solvent-free high-strength polyurethane cementing sealing glue and method for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594481A CN1594481A (en) | 2005-03-16 |
| CN1288221C true CN1288221C (en) | 2006-12-06 |
Family
ID=34663450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410024290 Expired - Fee Related CN1288221C (en) | 2004-06-24 | 2004-06-24 | Solvent-free high-strength polyurethane cementing sealing glue and method for making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1288221C (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008077270A1 (en) * | 2006-12-22 | 2008-07-03 | Jinhe Lin | Solvent-free polyurethane, its preparation and application |
| CN101265401B (en) * | 2008-04-23 | 2011-06-08 | 中国科学院广州化学研究所 | Method for preparing biomass polyurethane adhesive |
| CN101368079B (en) * | 2008-09-25 | 2012-05-09 | 广州鹿山新材料股份有限公司 | Fast-crystallization polyurethane hot melt adhesive and preparation method thereof |
| CN101638568B (en) * | 2009-06-09 | 2012-03-14 | 虞建放 | Modified polyurethane waterproof seal glue |
| CN101597460B (en) * | 2009-06-23 | 2012-05-30 | 天津开发区科泰化工新材料开发有限公司 | Special sealant surface layer coating for bottom of high-performance storage tank and preparation method thereof |
| CN101899279A (en) * | 2010-06-29 | 2010-12-01 | 山西省电力公司晋城供电分公司 | Method for preparing sealant for transmission equipment |
| CN101921564B (en) * | 2010-09-29 | 2012-04-04 | 泰州五行消防水带有限公司 | Special adhesive for aramid fiber braided layer and preparation method thereof |
| CN102020967B (en) * | 2010-11-17 | 2013-06-19 | 常州大学 | Preparation method of acrylic ester oligomer modified aqueous polyurethane pressure-sensitive adhesive |
| CN102108279B (en) * | 2010-12-17 | 2013-11-27 | 广西南宁齐顺化工有限公司 | Moisture curable polyurethane adhesive and preparation method thereof |
| CN102382612B (en) * | 2011-07-04 | 2013-01-09 | 淄博海特曼化工有限公司 | Single-component polyurethane adhesive sealing gum with hydrophobic performance and preparation method thereof |
| CN102277121B (en) * | 2011-07-04 | 2013-07-10 | 淄博海特曼化工有限公司 | Single-component moisture curing polyurethane sealant with heat-conducting property and preparation method thereof |
| CN102827569A (en) * | 2012-08-23 | 2012-12-19 | 江门亿源生化工程有限公司 | Quick-drying polyurethane adhesive with single component and no solvent and preparation method thereof |
| CN102796485A (en) * | 2012-09-11 | 2012-11-28 | 无锡市万力粘合材料有限公司 | Reactive polyurethane hot-melt adhesive and preparation method thereof |
| CN103398304B (en) * | 2013-07-23 | 2015-06-03 | 宁波市爱使电器有限公司 | Sealed LED lamp |
| CN103923595B (en) * | 2014-05-12 | 2015-12-02 | 谭宏伟 | No-solvent type color anti-skid road surface tamanori |
| CN104087234A (en) * | 2014-06-20 | 2014-10-08 | 安徽先锋门业科技有限公司 | Preparation method of high-strength polyurethane building sealing paste |
| CN104327789B (en) * | 2014-10-20 | 2016-10-05 | 穆瑜 | A kind of communication engineering construction high performance sealant |
| CN104388023A (en) * | 2014-10-31 | 2015-03-04 | 青岛昌安达药业有限公司 | Improved adhesive for waterproof coiled materials |
| CN104910849A (en) * | 2015-05-19 | 2015-09-16 | 安徽省华凯轻工科技有限公司 | High-tensile-strength polyurethane sealant and preparation method thereof |
| CN105062402B (en) * | 2015-07-17 | 2017-08-11 | 河南科技大学 | A kind of environmentally friendly sports field polyurethane glue and preparation method thereof |
| CN106065306A (en) * | 2016-06-08 | 2016-11-02 | 杭州阑氏道路工程技术有限公司 | A kind of novel bi-component antiskid road surface adhesive and preparation method thereof |
| CN106189985A (en) * | 2016-07-21 | 2016-12-07 | 柳州市五源科技有限公司 | Wood glue and preparation method thereof |
| CN106566456A (en) * | 2016-10-28 | 2017-04-19 | 无锡市永兴金属软管有限公司 | Metal corrugated pipe adhesive based on modification of nano-silicon dioxide, and preparation method thereof |
| CN106554746A (en) * | 2016-10-28 | 2017-04-05 | 无锡市永兴金属软管有限公司 | A kind of wavy metal pipe binder being modified based on sodium silicate and preparation method thereof |
| CN106543948A (en) * | 2016-10-28 | 2017-03-29 | 无锡市永兴金属软管有限公司 | A kind of wavy metal pipe binder based on montmorillonite/carbonization Si modification and preparation method thereof |
| CN106543946A (en) * | 2016-10-28 | 2017-03-29 | 无锡市永兴金属软管有限公司 | A kind of wavy metal pipe binder based on modifying nanometer cellulose and preparation method thereof |
| CN106590509A (en) * | 2016-12-01 | 2017-04-26 | 迪马新材料科技（苏州）有限公司 | High-viscosity and weather-resistant PUR adhesive and preparing method |
| CN107118730A (en) * | 2017-05-27 | 2017-09-01 | 江苏省江南新型复合研磨材料及制品工程技术研究中心有限公司 | A kind of blinds abrasive disk adhesive and preparation method thereof |
| CN107558327A (en) * | 2017-07-17 | 2018-01-09 | 江苏艺博防水防腐工程有限公司 | A kind of environmental protection flame retardant full-plastic plastic cement race track and its construction method |
| CN108300165B (en) * | 2017-12-29 | 2020-11-17 | 绍兴恒元机械制造有限公司 | Antirust and anticorrosive fitness equipment primer and preparation method thereof |
| CN108276949B (en) * | 2018-01-31 | 2021-03-23 | 广州吉必盛科技实业有限公司 | Two-component polyurethane pouring sealant and preparation method and use method thereof |
| CN109266292A (en) * | 2018-09-06 | 2019-01-25 | 深圳市德顺通科技有限公司 | A kind of environmental protection casting glue |
-
2004
- 2004-06-24 CN CN 200410024290 patent/CN1288221C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1594481A (en) | 2005-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1288221C (en) | Solvent-free high-strength polyurethane cementing sealing glue and method for making same | |
| CN1165592C (en) | Curable epoxy-based compositions | |
| CN1886479A (en) | Adhesive and sealant systems | |
| CN1194036C (en) | Application of heat-resistant rubber comosition | |
| CN100335576C (en) | Anti-corrosive paint of epoxy resin based on aqueous bitumen, and preparation method | |
| CN1317351C (en) | Improved adhesives for bonding composites | |
| CN1253477C (en) | Polymerization initiator systems and bonding compositions comprising vinyl aromatic compounds | |
| CN88101561A (en) | Improved compound glass window member with flexible isolating and black box | |
| CN1513907A (en) | Fluorine contained elastic composition | |
| CN1470550A (en) | Solidifying promotor, epoxy resin composition and semiconductor device | |
| CN1578819A (en) | Organoborane amine complex polymerization initiators and polymerizable compositions | |
| CN1930263A (en) | Resin composition and semiconductor devices made by using the same | |
| CN1035519A (en) | The moulding compound of thickening | |
| CN1142202C (en) | Thermosetting polyurethane resin and its making process | |
| CN1195038C (en) | Sealing agent and liquid crystal display element using the same | |
| CN1025204C (en) | Thermoplastic elastomer composition of fine heat adhesiveness | |
| CN1199412A (en) | Rubber compositions | |
| CN1594480A (en) | Silicane modified polyurethane cementing sealing glue and method for making same | |
| CN1293682A (en) | Novel polyisocyanate and process for producing the same | |
| CN1048391A (en) | The manufacture method of hard polyurethane foams | |
| CN1231519C (en) | Modified polyphenylene ether resin | |
| CN1122688C (en) | Double-compsn. polyurethane compsn. and its preparing method | |
| CN1403522A (en) | Composite adhesive specially for heat insulating polystyrene outer-wall board | |
| CN1094476C (en) | Formula and technology for producing colour concrete tiles with powdered coal ash and other waste industrial dregs | |
| CN1207334C (en) | Method for preparing silica suspension in optionally crosslinkable silicone matrix |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: ZIBO HITECMEN NEW MATERIAL + TECHNOLOGY CO., LTD. Free format text: FORMER NAME: ZIBO HITECMEN CHEMICAL CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 255088, No. 109-1, Tai Mo Road, hi tech Zone, Shandong, Zibo Patentee after: Zibo hitecmen new Mstar Technology Ltd Address before: 255088, No. 109-1, Tai Mo Road, hi tech Zone, Shandong, Zibo Patentee before: Zibo Hitecmen Chemical Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061206 Termination date: 20170624 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |