CN106243302B - Water blown inorganic hybridization polyurethane with melamine rigid foam material and its manufacture method - Google Patents
Water blown inorganic hybridization polyurethane with melamine rigid foam material and its manufacture method Download PDFInfo
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- CN106243302B CN106243302B CN201610626700.0A CN201610626700A CN106243302B CN 106243302 B CN106243302 B CN 106243302B CN 201610626700 A CN201610626700 A CN 201610626700A CN 106243302 B CN106243302 B CN 106243302B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3897—Low-molecular-weight compounds having heteroatoms other than oxygen containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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Abstract
Water blown inorganic hybridization polyurethane with melamine rigid foam material and its manufacture method, belong to the production of flame retardant polyurethane energy-saving material and energy-saving building technology field, with high temperature resistant inorganic hydridization melmac polyalcohol or inorganic hybridization polyalcohol etherificate melmac, emulsifying agent, composite catalyst, phosphate flame retardant, foaming agent, if water or waterglass are main raw material(s), it is agitated scattered, combined polyether is prepared respectively, then with isocyanates MDI in panel machine, flush coater, foam on casting machine, up to the full water foamed B1 grades of flame retardant inorganic hydridization polyurethane with melamine rigid foam material of environment-friendly type of the present invention.The rigid foam material of patent of the present invention does not contain low boiling hydrocarbon compound fluorochlorohydrocarbon and hydrochlorofluorocarbons class compound, with Water blown, ozone layer is not destroyed, does not produce greenhouse effects, environmental protection, fire resistance improves at least 20%, while physical property is ensured, excellent fireproof performance, its oxygen index (OI) is more than 30%.
Description
Technical field
The invention belongs to the production of flame retardant polyurethane energy-saving material and energy-saving building technology field, the more particularly to poly- ammonia of Water blown
Ester rigid foam material and its manufacture method.
Background technology
China is the big country of a climate characteristic complexity, such as the Northeast of severe cold, the River of summer hot cold,
This make it that the energy consumption of China's building materials is very big.Winter warming of northern area etc., its energy consumption account for national total energy consumption
27.3%.But the problem of due to material, technology and technique, China's traditional architecture unit area heating energy consumption are weathers in the world
2-3 times of developed country similar in condition.What country promulgated《Energy saving medium-term and long-term ad hoc planning》Provide that Lao is " new during 13, five "
Building wants strict implement energy conservation standard, while adiabatic heat-insulation transformation is progressively implemented to existing building.65% is carried out comprehensively
75% energy conservation standard is carried out in energy conservation standard, a line city.
The heat insulating energy saving material that China uses at present mainly includes following several：Foam type thermal insulation material, composition silicate
Thermal insulation material, heat-insulating calcium silicate product thermal insulation material.
The foam type thermal insulation material used at home is mainly EPS thermal insulation materials；And polyurethane (PU) thermal insulation material and EPS
Thermal insulation material is compared, and thermal conductivity factor is lower, and the heat insulation effect of the PU rigid foams of 50mm thickness is equivalent to 80-100mm thickness
EPS.When particularly realizing energy saving 65% in north cold area, EPS seam leaks, there are serious freeze thawing phenomenon, comes off existing
As serious.
Ordinary rigid polyurethane foam plastics is generally using low boiling hydrocarbon compound fluorochlorohydrocarbon (F11,141B) as hair
Infusion, but discovered in recent years such compound is to destroy the arch-criminal of earth's ozone layer.Hydrochlorofluorocarbons (HCFC) class also has one
Fixed ozone remove function and generation greenhouse effects, so original polyurethane foam system must be substituted, therefore full water hair
Bubble technology increasingly receives the favor of people.
And common Water-Blown Rigid Polyurethane Foams are there are many deficiencies, as system viscosity is too big, poor fluidity,
Foaming is uneven and causes abscess thick, and thermal conductivity factor is bigger than normal, foams embrittlement etc..
The content of the invention
In order to solve the above problem existing in the prior art, the present invention provides a kind of Water blown polyurethane with melamine is hard
Foam material and its manufacture method.With high temperature resistant inorganic hydridization melmac polyalcohol or inorganic hybridization polyalcohol etherificate trimerization
Melamine resin, emulsifying agent, composite catalyst, phosphate flame retardant, foaming agent, if water or waterglass are main raw material(s), through stirring
Mix it is scattered, prepare respectively full water foamed B1 grades of flame melamine polyurethane plate, spraying, cast combined polyether, then with it is different
Cyanate MDI foams on panel machine, flush coater, casting machine, up to the full water foamed B1 grades of flame retardant inorganic of environment-friendly type of the present invention
Hydridization polyurethane with melamine rigid foam material.
The technical solution adopted in the present invention is as follows：
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Inorganic hybridization melmac polyalcohol
Or
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Inorganic hybridization melmac polyalcohol
The emulsifying agent is silicone oil, and the silicone oil is hard bubble silicone oil.
The composite catalyst is potassium acetate, five methyl diethylentriamine, 1,3,5- tri- (dimethylamino-propyl) hexahydro
Triazine, trimethyl-N-2 hydroxypropyls caproic acid, triethylenediamine, N, two in accelerine or dibutyl tin laurate
Kind is several.
The fire retardant is phosphate, and the phosphate is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, tricresyl phosphate (2,3- dichloros
One or both of propyl group) ester, the viscosity of the phosphate is less than 300Pas.
The inorganic hybridization melmac polyol molecule structure is as follows：
X in the molecular structure is one kind in inorganic hybridization element, including B or Sb；
R in the molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
- (OCH2CH2CH2CH3)kOH or-O (CH2)pCH(OH)CH2OH wherein 2≤n≤6,2≤m≤6,2≤p≤6,2
≤k≤41。
The inorganic hybridization polyalcohol etherificate melmac molecular structure is as follows：
X in the molecular structure is one kind in inorganic hybridization element, including B or Sb；
R in the molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
- (OCH2CH2CH2CH3)kOH or-O (CH2)pCH(OH)CH2OH, wherein 2≤n≤6,2≤m≤6,2≤p≤6,2
≤k≤41。
The manufacture method of Water blown inorganic hybridization polyurethane with melamine rigid foam material, it is characterised in that：Including following tool
Body step：
(1) combined polyether is prepared
Formula components in claim 1 are added separately in mixing kettle, stirring at normal temperature disperse 2-4 it is small when, filter out micro-
Mechanical admixture is measured, obtains Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate by
According to weight ratio 1：(1-1.8) is matched, and is foamed on panel machine, flush coater, casting machine, and it is inorganic miscellaneous to obtain Water blown
Change polyurethane with melamine rigid foam material.
The above-mentioned technical proposal of the present invention compared with prior art, has the following advantages：
1st, the rigid foam material of patent of the present invention does not contain low boiling hydrocarbon compound fluorochlorohydrocarbon and hydrochlorofluorocarbons class compound,
With Water blown, ozone layer is not destroyed, does not produce greenhouse effects, environmental protection, while employ the three of inorganic hybridization during material preparation
Cymel polyalcohol, the introducing of inorganic hybridization element improve fire resistance, compared with the resin before non-hydridization, resistance to height
Warm nature can improve more than 50 DEG C, and fire resistance improves at least 20%, while physical property is ensured, excellent fireproof performance,
Its oxygen index (OI) is more than 30%, meets the B1 grades of requirements of GB8624-2012 standards.
2nd, the manufacturing method of the present invention utilizes low viscosity phosphate to B1 grades of flame melamine polyurethane compositions of Water blown
Polyethers is effectively diluted, and it is too big to overcome water-blown polyurethane combined polyether viscosity, poor fluidity, and foaming is uneven and causes
Abscess is thick, and thermal conductivity factor is bigger than normal, the defects such as foams embrittlement, intensity are low.The phosphorus source of phosphorus-nitrogen flame-retardant system is provided at the same time, is carried
The high fire resistance of full water foamed polyurethane with melamine foamed material.
3rd, the present invention utilizes low viscosity phosphate, effectively improves full water foamed B1 grades of flame melamine polyurethane group
Close the viscosity of polyethers so that full water foamed B1 grades of flame melamine polyurethane rigid foam materials of the invention can spray, can be with
Poured into a mould with casting machine, high pressure panel machine can be used to be molded, thermal insulation material is made.
4th, the polyurethane rigid foam material of patent manufacture of the present invention, it is not necessary to use expensive high fire-retardance organic phosphate flame-retardant
Agent, makes the reduction of foam cost greatly, reduces more than 30%, economy is more reasonable.
5th, expanded material of the invention is compared with similar product has obvious technical advantage and economic advantages, is saved for building
Environmental protection, B1 grades of thermal insulation materials fire-retardant, invention is waterproof integrated can be provided.Can be in building field, petrochemical industry, freezer
Widely used in the fields such as cold insulation, great economic benefit will be produced, while country is completed to perform Montreal Agreement plan,
Atmospheric warming effect is reduced, protection atmospheric ozone layer has huge social benefit.
Embodiment
With reference to specific embodiment, the present invention will be described in detail, but the invention is not limited in specific embodiment.
Embodiment 1
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, inorganic hybridization polyurethane with melamine combined polyether, by weight
Portion rate is measured, formula is as follows：
Emulsifying agent is hard bubble silicone oil.
Composite catalyst is potassium acetate and five methyl diethylentriamine.
Fire retardant is phosphate, and phosphate is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, and the viscosity of phosphate is 290Pas.
Inorganic hybridization melmac polyalcohol is specially boron hydridization melmac propane diols, its molecular structural formula
And preparation method is as follows：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 2.5 to add acid for adjusting pH, at 35 DEG C
Under conditions of, mixing speed is 60 revs/min, and insulation 120min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
Stirred under the conditions of 40 revs/min of rotating speed, it is 8.0 to add alkali to adjust pH, which keeps temperature to be less than 50
℃；
(3) hydridization is reacted
Four water, eight Boratex and water are added into reaction kettle, be warming up to 100 DEG C reaction 2 it is small when, under conditions of 80 DEG C, often
Pressure steam methanol, under conditions of 100 DEG C, vacuum be 0.090MPa under the conditions of steam water, to water content reach 0.5% with
Under；
(4) cold filtration
60 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtain boron hydridization etherified melamine
Polyimide resin；
(5) ether exchange reaction
Propane diols, and hydrochloric acid are added, at 100 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure,
The methanol quality steamed to metering reaches theoretical amount, and ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum 0.090MPa, 95 DEG C of temperature, the methanol of remaining is steamed, room temperature is cooled to, that is, obtains boron
Hydridization melmac propane diols, yield 99.0%.
The manufacture method of above-mentioned Water blown inorganic hybridization polyurethane with melamine rigid foam material, it is characterised in that：Including with
Lower specific steps：
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components are added separately in mixing kettle, room temperature stirs
Mix scattered 2 it is small when, filter out micro mechanical admixture, obtain Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate by
According to weight ratio 1：1 is matched, and is foamed on panel machine, flush coater, casting machine, obtains Water blown inorganic hybridization melamine
Amine polyurethane rigid foam material.
Embodiment 2
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Emulsifying agent is hard bubble silicone oil.
Composite catalyst for five methyl diethylentriamine, 1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazine, trimethyl-
N-2 hydroxypropyls caproic acid and dibutyl tin laurate.
Fire retardant is phosphate, and phosphate is tricresyl phosphate (2,3- bis- chloropropyl) ester, and the viscosity of phosphate is 285Pas.
Inorganic hybridization melmac polyalcohol is specially molybdenum hydridization melmac glycerine
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 5.0 to add nitre acid for adjusting pH, 50
Under conditions of DEG C, mixing speed is 70 revs/min, and insulation 100min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
Stirred under the conditions of 70 revs/min of rotating speed, it is 8.6 to add alkali to adjust pH, which keeps temperature to be less than 50
℃；
(3) hydridization is reacted
Sodium molybdate and water are added into reaction kettle, be warming up to 105 DEG C of reactions 1.5 it is small when, under conditions of 90 DEG C, normal pressure steams
Go out methanol, under conditions of 105 DEG C, steam water under the conditions of vacuum is 0.095MPa, reach less than 0.5% to water content；
(4) cold filtration
70 DEG C are cooled to, 2.5% super-cell is added, salt is filtered out with filter, obtains molybdenum hydridization etherificate trimerization
Melamine resin；
(5) ether exchange reaction
Glycerine, and nitric acid are added, at 105 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure,
The methanol quality steamed to metering reaches theoretical amount, and ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum 0.1MPa, 105 DEG C of temperature, the methanol of remaining is steamed, room temperature is cooled to, that is, obtains inorganic
Hydridization melmac polyalcohol, yield 98.0%.
The manufacture method of above-mentioned Water blown inorganic hybridization polyurethane with melamine rigid foam material, it is characterised in that：Including with
Lower specific steps：
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components are added separately in mixing kettle, room temperature stirs
Mix scattered 4 it is small when, filter out micro mechanical admixture, obtain Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate by
According to weight ratio 1：1.8 are matched, and are foamed on panel machine, flush coater, casting machine, obtain Water blown inorganic hybridization trimerization
Cyanamide polyurethane rigid foam material.
Embodiment 3
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Emulsifying agent is hard bubble silicone oil.
Composite catalyst is 1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazine, triethylenediamine and N, N- dimethyl benzene
Amine.
Fire retardant is phosphate, and phosphate is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester and tricresyl phosphate (2,3- bis- chloropropyl) ester,
The viscosity of phosphate is 269Pas.
Inorganic hybridization polyalcohol etherificate melmac is specially stilba diethylene glycol etherificate melmac, its
Molecular structural formula and preparation method are as follows：
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and diethylene glycol are added in reaction kettle according to the above ratio, it is 5.5 to add acid for adjusting pH,
Under conditions of 65 DEG C, mixing speed is 80 revs/min, and insulation 30min carries out etherification reaction, obtains diethylene glycol etherificate melamine
Polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 80 revs/min of rotating speed, it is 9.0 to add alkali to adjust pH, which keeps temperature low
In 50 DEG C；
(3) hydridization is reacted
Antimony oxide and water are added into reaction kettle, be warming up to 110 DEG C of reactions 0.5 it is small when, hydridization reaction is completed；
(4) distillation removes remaining polyalcohol
Under conditions of vacuum 0.1MPa, 100 DEG C of temperature, the remaining diethylene glycol added in step (1) is steamed；
(5) cold filtration
80 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtain stilba diethylene glycol
Etherified melamine polyimide resin, yield 98.5%.
The manufacture method of above-mentioned Water blown inorganic hybridization polyurethane with melamine rigid foam material, it is characterised in that：Including with
Lower specific steps：
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components are added separately in mixing kettle, room temperature stirs
Mix scattered 3 it is small when, filter out micro mechanical admixture, obtain Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate by
According to weight ratio 1：1.4 are matched, and are foamed on panel machine, flush coater, casting machine, obtain Water blown inorganic hybridization trimerization
Cyanamide polyurethane rigid foam material.
Embodiment 4
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Emulsifying agent is hard bubble silicone oil.
Composite catalyst is 1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazine, trimethyl-N-2 hydroxypropyls caproic acid, Sanya
Ethyldiamine, N, accelerine and dibutyl tin laurate
Fire retardant is phosphate, and phosphate is tricresyl phosphate (2,3- bis- chloropropyl) ester, and the viscosity of phosphate is 280Pas.
Inorganic hybridization melmac polyalcohol is specially boron hydridization melmac pentaerythrite, its molecular structure
It is as follows with preparation method：
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 3.5 to add salt acid for adjusting pH, 55
Under conditions of DEG C, mixing speed is 70 revs/min, and insulation 80min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
Stirred under the conditions of 60 revs/min of rotating speed, it is 8.5 to add alkali to adjust pH, which keeps temperature to be less than 50
℃；
(3) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, be warming up to 105 DEG C of reactions 1 it is small when, under conditions of 90 DEG C,
Normal pressure steams methanol, under conditions of 100 DEG C, steams water under the conditions of vacuum is 0.090MPa, reaches 0.5% to water content
Below；
(4) cold filtration
70 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtain boron hydridization etherified melamine
Polyimide resin；
(5) ether exchange reaction
Pentaerythrite is added, and hydrochloric acid carries out ether exchange reaction at 105 DEG C, and the methanol of generation is constantly steamed under normal pressure,
The methanol quality steamed to metering reaches theoretical amount, and ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum 0.090MPa, 100 DEG C of temperature, the methanol of remaining is steamed, room temperature is cooled to, that is, obtains nothing
Machine hydridization melmac polyalcohol, yield 98.0%.
The manufacture method of above-mentioned Water blown inorganic hybridization polyurethane with melamine rigid foam material, it is characterised in that：Including with
Lower specific steps：
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components are added separately in mixing kettle, room temperature stirs
Mix scattered 2 it is small when, filter out micro mechanical admixture, obtain Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate by
According to weight ratio 1：1 is matched, and is foamed on panel machine, flush coater, casting machine, obtains Water blown inorganic hybridization melamine
Amine polyurethane rigid foam material.
Embodiment 5
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Emulsifying agent is hard bubble silicone oil.
Composite catalyst is potassium acetate, trimethyl-N-2 hydroxypropyls caproic acid, triethylenediamine and N, accelerine.
Fire retardant is phosphate, and phosphate is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester and tricresyl phosphate (2,3- bis- chloropropyl)
Ester, the viscosity of phosphate is 289Pas.
Inorganic hybridization polyalcohol etherificate melmac is specially stilba diethylene glycol etherificate melmac, its
Molecular structure and preparation method are as follows：
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and diethylene glycol are added in reaction kettle according to the above ratio, it is 5.5 to add acid for adjusting pH,
Under conditions of 65 DEG C, mixing speed is 80 revs/min, and insulation 30min carries out etherification reaction, obtains diethylene glycol etherificate melamine
Polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 80 revs/min of rotating speed, it is 9.0 to add alkali to adjust pH, which keeps temperature low
In 50 DEG C；
(3) hydridization is reacted
Antimony oxide and water are added into reaction kettle, be warming up to 110 DEG C of reactions 0.5 it is small when, hydridization reaction is completed；
(4) distillation removes remaining polyalcohol
Under conditions of vacuum 0.1MPa, 100 DEG C of temperature, the remaining diethylene glycol added in step (1) is steamed；
(5) cold filtration
80 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtain stilba diethylene glycol
Etherified melamine polyimide resin, yield 98.5%.
The manufacture method of above-mentioned Water blown inorganic hybridization polyurethane with melamine rigid foam material, it is characterised in that：Including with
Lower specific steps：
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components are added separately in mixing kettle, room temperature stirs
Mix scattered 3 it is small when, filter out micro mechanical admixture, obtain Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate by
According to weight ratio 1：1.5 are matched, and are foamed on panel machine, flush coater, casting machine, obtain Water blown inorganic hybridization trimerization
Cyanamide polyurethane rigid foam material.
Embodiment 6
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
Water blown inorganic hybridization polyurethane with melamine rigid foam material, the material are by inorganic hybridization polyurethane with melamine
Combined polyether and polymeric isocyanate foam the rigid foam material to be formed, it is characterised in that：
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Emulsifying agent is hard bubble silicone oil.
Composite catalyst is potassium acetate, trimethyl-N-2 hydroxypropyls caproic acid and triethylenediamine.
Fire retardant is phosphate, and phosphate is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, and the viscosity of phosphate is 276Pas.
Inorganic hybridization polyalcohol is etherified melmac
The preparation of molybdenum hydridization glycerine etherified melamine polyimide resin
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and glycerine are added in reaction kettle according to the above ratio, it is 4.5 to add acid for adjusting pH, 40
Under conditions of DEG C, mixing speed is 65 revs/min, and insulation 90min carries out etherification reaction, obtains glycerine etherified melamine amine tree
Fat；
(2) alkali neutralization
It is stirred under the conditions of 70 revs/min of rotating speed, it is 8.5 to add alkali to adjust pH, which keeps temperature low
In 50 DEG C；
(3) hydridization is reacted
Sodium molybdate and water are added into reaction kettle, be warming up to 105 DEG C of reactions 1.5 it is small when, hydridization reaction is completed；
(4) distillation removes remaining polyalcohol
Under conditions of vacuum 0.1MPa, 120 DEG C of temperature, the remaining glycerine added in step (1) is steamed；
(5) cold filtration
75 DEG C are cooled to, 2% super-cell is added, salt is filtered out with filter, obtains molybdenum hydridization glycerine etherificate
Melmac, yield 98.2%.
The manufacture method of above-mentioned Water blown inorganic hybridization polyurethane with melamine rigid foam material, it is characterised in that：Including with
Lower specific steps：
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components are added separately in mixing kettle, room temperature stirs
Mix scattered 4 it is small when, filter out micro mechanical admixture, obtain Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate by
According to weight ratio 1：1.8 are matched, and are foamed on panel machine, flush coater, casting machine, obtain Water blown inorganic hybridization trimerization
Cyanamide polyurethane rigid foam material.
Claims (5)
1. Water blown inorganic hybridization polyurethane with melamine rigid foam material, which is by inorganic hybridization polyurethane with melamine group
Polyethers and polymeric isocyanate is closed to foam the rigid foam material to be formed, it is characterised in that：
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Inorganic hybridization melmac polyalcohol
Or
The inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula are as follows：
Inorganic hybridization melmac polyalcohol
The inorganic hybridization melmac polyol molecule structure is as follows：
X in the molecular structure is one kind in inorganic hybridization element, including B or Sb；
R in the molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
- (OCH2CH2CH2CH3)kOH or-O (CH2)pCH(OH)CH2OH wherein 2≤n≤6,2≤m≤6,2≤p≤6,2≤k≤
41；
The inorganic hybridization polyalcohol etherificate melmac molecular structure is as follows：
X in the molecular structure is one kind in inorganic hybridization element, including B or Sb；
R in the molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
- (OCH2CH2CH2CH3)kOH or-O (CH2)pCH(OH)CH2OH, wherein 2≤n≤6,2≤m≤6,2≤p≤6,2≤k
≤41。
2. Water blown inorganic hybridization polyurethane with melamine rigid foam material as claimed in claim 1, it is characterised in that：The breast
Agent is silicone oil, and the silicone oil is hard bubble silicone oil.
3. Water blown inorganic hybridization polyurethane with melamine rigid foam material as claimed in claim 1, it is characterised in that：It is described multiple
Conjunction catalyst is potassium acetate, five methyl diethylentriamine, 1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazine, trimethyl-N-2
Two or more in hydroxypropyl caproic acid, triethylenediamine, N, accelerine or dibutyl tin laurate.
4. Water blown inorganic hybridization polyurethane with melamine rigid foam material as claimed in claim 1, it is characterised in that：The resistance
Combustion agent is phosphate, and the phosphate is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, one kind in tricresyl phosphate (2,3- bis- chloropropyl) ester
Or two kinds, the viscosity of the phosphate is less than 300Pas.
5. the manufacture method of Water blown inorganic hybridization polyurethane with melamine rigid foam material as claimed in claim 1, its feature
It is：Including step in detail below：
(1) combined polyether is prepared
Formula components in claim 1 are added separately in mixing kettle, stirring at normal temperature disperse 2-4 it is small when, filter out micro machine
Tool impurity, obtains Water blown inorganic hybridization polyurethane with melamine combined polyether；
(2) foam
By the Water blown inorganic hybridization polyurethane with melamine combined polyether obtained in step (1) and polymeric isocyanate according to weight
Measure ratio 1：(1-1.8) is matched, and is foamed on panel machine, flush coater, casting machine, obtains Water blown inorganic hybridization trimerization
Cyanamide polyurethane rigid foam material.
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| CN201610626700.0A CN106243302B (en) | 2016-08-01 | 2016-08-01 | Water blown inorganic hybridization polyurethane with melamine rigid foam material and its manufacture method |
| PCT/CN2017/078239 WO2018023986A1 (en) | 2016-08-01 | 2017-03-26 | Water-blown rigid inorganic hybrid melamine polyurethane foam material and preparation method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610626700.0A CN106243302B (en) | 2016-08-01 | 2016-08-01 | Water blown inorganic hybridization polyurethane with melamine rigid foam material and its manufacture method |
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| CN106243302B true CN106243302B (en) | 2018-04-17 |
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| CN106243302B (en) * | 2016-08-01 | 2018-04-17 | 常州聚博节能科技有限公司 | Water blown inorganic hybridization polyurethane with melamine rigid foam material and its manufacture method |
| CN106432672A (en) * | 2016-09-07 | 2017-02-22 | 张家港迪蒙德节能科技有限公司 | All-water-blown rigid polyurethane foam material and production method thereof |
| CN108752033A (en) * | 2018-05-20 | 2018-11-06 | 滨州市神华建材有限公司 | New type coal rock mass inorganic compounding rigid foam material |
| CN109749037A (en) * | 2018-11-19 | 2019-05-14 | 扬州恒丰塑胶有限责任公司 | A kind of high resistant combustible polyether glycol, hard polyurethane foam and its preparation method and application |
| CN111732816A (en) * | 2020-06-18 | 2020-10-02 | 浙江亚迪纳新材料科技股份有限公司 | Preparation process of light high-water-locking modified melamine foam plastic |
| CN113354794A (en) * | 2021-05-25 | 2021-09-07 | 苏州恒利峰节能建材科技有限公司 | Full-water-blown flame-retardant polyurethane and foamed ceramic composite thermal insulation material and preparation method thereof |
| CN115109218A (en) * | 2022-06-26 | 2022-09-27 | 瀚寅(苏州)新材料科技有限公司 | Flame-retardant combined polyether and preparation method thereof |
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| CA2441246A1 (en) * | 2002-09-23 | 2004-03-23 | Hilti Aktiengesellschaft | Two-component foam system for producing constructional foams and their use |
| US7700661B2 (en) * | 2005-05-05 | 2010-04-20 | Sleep Innovations, Inc. | Prime foam containing vegetable oil polyol |
| CN101812174B (en) * | 2010-04-01 | 2011-11-16 | 湖州创新聚氨酯科技有限公司 | Difficult-flammble polymer polyether glycol with high solid content and low viscosity as well as preparation method and application thereof |
| CN102295616B (en) * | 2011-05-18 | 2013-09-04 | 杨彦威 | Amino resin having polyhydroxy structure, and preparation method thereof |
| US20140066532A1 (en) * | 2012-09-06 | 2014-03-06 | Bayer Materialscience Llc | Rigid foams suitable for wall insulation |
| CN103739821A (en) * | 2013-12-20 | 2014-04-23 | 苏州市万泰真空炉研究所有限公司 | Preparation method of novel carbon fiber reinforced type polyurethane rigid foam plastic |
| CN104130368B (en) * | 2014-07-21 | 2016-09-21 | 万华节能科技集团股份有限公司 | A kind of flame retardant polyurethane cast rigid foam sheet material |
| CN104262566A (en) * | 2014-09-09 | 2015-01-07 | 上海应用技术学院 | Flame-retardant polyurethane hard foam containing nitrogen intrinsic structure and preparation method thereof |
| CN104262567B (en) * | 2014-09-09 | 2017-01-11 | 上海应用技术学院 | Flame-retardant polyurethane rigid foam taking melamine as basic characteristic and preparation method of flame-retardant polyurethane rigid foam |
| CN104987484A (en) * | 2015-05-29 | 2015-10-21 | 张家港迪蒙德节能科技有限公司 | Inorganic material hybrid hard melamine polyurethane foam heat insulation material, preparation method thereof and combined polyether used therein |
| CN106243302B (en) * | 2016-08-01 | 2018-04-17 | 常州聚博节能科技有限公司 | Water blown inorganic hybridization polyurethane with melamine rigid foam material and its manufacture method |
| CN106432672A (en) * | 2016-09-07 | 2017-02-22 | 张家港迪蒙德节能科技有限公司 | All-water-blown rigid polyurethane foam material and production method thereof |
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