CN109679564A - Fluorinated silicone modified flame retardant polyurethane hot melt adhesive and preparation method thereof - Google Patents
Fluorinated silicone modified flame retardant polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109679564A CN109679564A CN201811476163.1A CN201811476163A CN109679564A CN 109679564 A CN109679564 A CN 109679564A CN 201811476163 A CN201811476163 A CN 201811476163A CN 109679564 A CN109679564 A CN 109679564A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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Abstract
The invention discloses a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive and preparation method thereof, feature is the polyether Glycols for including 1~15 part, 1~30 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~30 part of crystalline polyester dihydric alcohol, 5~40 parts of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object, 10~50 parts of isocyanates, 0.1~1 part of catalyst, 0.1~1 part of antioxidant and 0.1~2 part of silane coupling agent.Elder generation's synthesis of hydroxy of the present invention blocks phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object, its chemical structure is: hydroxy-end capped poly- (acrylic acid trifluoro ethyl ester-is random-methacryloxypropyl list sealing end dimethyl polysiloxane-is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of butyl acrylate -), fluorine silicon segment and reactive flame retardant are introduced in base polyurethane prepolymer for use as, can further promote waterproof performance, chemical resistance and the flame retardant property of polyurethane gel.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive and its preparation
Method, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry, wood material processing and families
Have industry isostructuralism and is bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use, environmentally friendly, and performance again can be with
Solvent-based thermal melten gel compares favourably.Nearly ten years, polyurethane hot melt is obtained in the high-end fields such as electronics and appliance industry, automobile industry
It is fast-developing and be widely used.Polyurethane hot melt can be divided into thermoplastic polyurethane elastomer hot melt adhesive by cured form difference
And reactive polyurethane hot melt, reactive polyurethane hot melt can be divided into wet-cured type and closing by its principle of solidification difference
Type；Research of Moisture-curable Polyurethane Hot-melt Adhesive PUR is a kind of one pack system hot melt adhesive, is melted after heating, and flows scatter coated in substrate
Surface cools down after adherend bonding and forms excellent first adhesive property, then due to substrate surface contain micro-moisture or its
His compound containing active hydrogen reacts with isocyano (- NCO) and chemical crosslink reaction occurs, thus generate have it is highly cross-linked
A kind of structural bonding hot melt adhesive of network and cohesive force greatly.
Research of Moisture-curable Polyurethane Hot-melt Adhesive has technically obtained unprecedented development at present, low mainly around high-adhesive-strength
Melt viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised.Chinese patent discloses a kind of entitled
The application for a patent for invention of " a kind of reactive hot melt adhesive ", application number are 201480080313.0, prepare it is a kind of have return
The removable polyurethane-hot melt adhesive repaired, more suitable for high-end electronic product scope application.Chinese patent also discloses one
The application for a patent for invention of kind entitled " solvent-free damp solidifying polyurethane hot-melt adhesive composition ", application number are
201180047316.0, prepare a kind of quick polyurethane-hot melt for establishing adhesive property polyacrylate and polyester preparation of low toxicity
Viscose binder.In order to improve the cured form of Research of Moisture-curable Polyurethane Hot-melt Adhesive, it is " a kind of that Chinese patent, which discloses a kind of title,
The application for a patent for invention of organic silicon modified polyurethane sealant ", application number are 201710271725.8, prepare a kind of organosilicon
Modified polyurethane sealant replaces isocyano (- NCO) with silane coupling agent, is more suitable for applying under high humidity environment.Currently, wet
The research and development technology of curable polyurethane hot-melt glue meets different type high-end electronic product scope application in fast development.It is wet solid
Although highly cross-linked network can be formed after hardening by changing type polyurethane hot melt adhesive, resistance to there is also waterproof performance, solvent resistant
Ageing properties and heat resistance deficiency problem.This main cause is most of Research of Moisture-curable Polyurethane Hot-melt Adhesive at the beginning of in order to improve it
Sticky energy joined a large amount of non-reacted thermoplasticity thickening resin or polynary acrylic copolymer.These non-reaction systems increase
Viscous resin can not participate in solidification and generate cross-linked network, to easily reduce the waterproof performance of polyurethane hot melt adhesive coating, chemicals-resistant
Performance, heat resistance and ageing-resistant performance etc..
Summary of the invention
There is provided the purpose of the present invention is overcome the deficiencies in the prior art a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive and
Preparation method is improved since fluorinated silicone modified flame retardant polyurethane hot melt adhesive is by fluorinated silicone modified and introducing reactive flame retardant
Waterproof performance, chemical resistance, flame retardant property, heat resistance of polyurethane coating etc..
In order to achieve the above object, the technical solution of fluorinated silicone modified flame retardant polyurethane hot melt adhesive of the invention is realized in
, it is characterised in that including 1~15 part of polyether Glycols, 1~30 part of liquid polyesters dihydric alcohol, 1~40 part fire-retardant poly-
Ethoxylated polyhydric alcohol, 1~30 part of crystalline polyester dihydric alcohol, 5~40 parts of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer
Object, 10~50 parts of isocyanates, 0.1~1 part of catalyst, 0.1~1 part of antioxidant and 0.1~2 part it is silane coupled
Agent is mass fraction above；The chemical structure of the hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is: hydroxyl envelope
Hold it is poly- (acrylic acid trifluoro ethyl ester-is random-methacryloxypropyl list sealing end dimethyl polysiloxane-is random-acrylic acid fourth
Random -2- methyl -2- 2-hydroxyethyl acrylate the phosphate of ester -) i.e. P(TFMA-r-BAPDMS-r-BA-r-HMP), hydroxyl envelope
1~2 hydroxy functional group is contained in end phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object each macromolecular chain end that is averaged, hydroxy-end capped to contain
The number-average molecular weight of phosphorus flame-retardant polypropylene olefin(e) acid fluorine-silicon copolymer object is 1000~50000.
In the technical scheme, the polyether Glycols are polyoxypropyleneglycol of the number-average molecular weight 500~4000
One or two kinds of any combination of PPG or polytetrahydrofuran ether glycol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42.
In order to achieve the above object, the technical solution of the preparation method of fluorinated silicone modified flame retardant polyurethane hot melt adhesive of the invention
It is achieved in that it is characterized in that preparation step is as follows:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
1~20 part of acrylic acid trifluoro ethyl ester TFMA, 1~20 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~50 part of butyl acrylate BA and 5~25 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP
It is dissolved in 50~100 parts of toluene, is controlled in 40~100 DEG C, under nitrogen protection, 0.1~3 part of thermal initiator 4 is added,
4'- azo is bis- (4- cyano amylalcohol), polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtains hydroxy-end capped phosphorous
Flame-retardant polypropylene olefin(e) acid fluorine-silicon copolymer object, the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is 1000~
50000；
Step 2: fluorinated silicone modified flame retardant polyurethane hot melt adhesive is synthesized
1~15 part of polyether Glycols, 1~30 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~30
The hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object of one synthesis of the step of crystalline polyester dihydric alcohol of part, 5~40 parts,
After 0.1~1 part of catalyst and the mixing of 0.1~1 part of antioxidant, 120~150 DEG C are calorified, it is small to vacuumize water removal about 1~3
When, until the water content of mixture is lower than 280ppm, cool down in 70~100 DEG C, under nitrogen protection, is added 10~50 parts
Isocyanates carries out polymerization reaction 1~5 hour, and sampling analysis polymerizate NCO% content reaches 1%~3%, and viscosity reaches 3000
~15000 mPa.s are added 0.1~2 part of silane coupling agent, obtain fluorinated silicone modified flame retardant polyurethane hot melt adhesive, be above
Mass fraction.
In the technical scheme, the methacryloxypropyl list in step 1 blocks dimethyl polysiloxane
The number-average molecular weight of MAPDMS is 1000, No. CAS: 146632-07-7.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity.
Compared with prior art, the present invention have following advantages and effects
1, the present invention improves polyurethane adhesive by introducing fluorine silicon segment and reactive flame retardant in base polyurethane prepolymer for use as
The waterproof of body, chemicals-resistant, fire-retardant etc.；
2, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, is improved thickening resin and is gathered
The compatibility of urethane further solves Research of Moisture-curable Polyurethane Hot-melt Adhesive solvent resistance；
3, the present invention solves the problems, such as that traditional Research of Moisture-curable Polyurethane Hot-melt Adhesive is poor to substrate wet performance, improves hot melt adhesive
The flow leveling of sizing, packaging and Process of Applying Glue are not likely to produce bubble.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
6 parts of acrylic acid trifluoro ethyl ester TFMA, 6 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 30 parts of butyl acrylate BA and 5 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 50 parts
Toluene in, be controlled in 60 DEG C, under nitrogen protection, 2.5 parts of thermal initiator 4 be added, 4'- azo is bis- (4- cyano amylalcohol),
Polymerization reaction 5 hours, after rotary evaporation removes toluene,
Obtain the i.e. P(TFMA-r-BAPDMS-r-BA-r-HMP of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object), hydroxyl
1~2 hydroxy functional group is contained in sealing end phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object each macromolecular chain end that is averaged, hydroxy-end capped
The number-average molecular weight of phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is 8000；Methacryloxypropyl list blocks the poly- silicon of dimethyl
Oxygen alkane MAPDMS
Number-average molecular weight be 1000, No. CAS: 146632-07-7.
Step 2: fluorinated silicone modified flame retardant polyurethane hot melt adhesive is synthesized
5 parts of polyoxypropyleneglycol PPG, 10 parts of polyethylene glycol adipate glycol PEA, 20 parts of flame retarding polyether is polynary
Alcohol WANOL FR-130, the hydroxy-end capped phosphor-containing flame-proof of 15 parts of 7360,25 parts of step 1 of crystalline polyester dihydric alcohol synthesis are poly-
After acrylic acid fluorine-silicon copolymer object, 0.2 part of phosphoric acid and the mixing of 0.4 part of irgasfos 168,120 DEG C are calorified, water removal 2 is vacuumized
Hour, until the water content of mixture is lower than 280ppm, cool down in 80 DEG C, under nitrogen protection, 25 parts of modification two is added
4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of phenylmethane -), it carries out polymerization reaction 3 hours, sampling analysis is poly-
It closes product NCO% content and reaches 1.5%, viscosity reaches 5210 mPa.s, 0.5 part of silane coupling agent ND-42 is added, obtains fluorine
Si modification flame retardant polyurethane hot melt adhesive, is mass fraction above.The number-average molecular weight of polyoxypropyleneglycol PPG is 1000,
The number-average molecular weight of polyethylene glycol adipate glycol PEA is 500, with Brookfield DV-C digital viscometer viscosity,
Test setting temperature is 100 DEG C.
Embodiment two
It is a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
10 parts of acrylic acid trifluoro ethyl ester TFMA, 10 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 35 parts of butyl acrylate BA and 10 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 80
In the toluene of part, 65 DEG C are controlled in, under nitrogen protection, 1.5 parts of thermal initiator 4, bis- (the 4- cyano penta of 4'- azo are added
Alcohol), polymerization reaction 10 hours, after rotary evaporation removes toluene, obtain hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
That is P(TFMA-r-BAPDMS-r-BA-r-HMP), average each big point of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
1~2 hydroxy functional group is contained in subchain end, and the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is
18300；Methacryloxypropyl list block dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
Step 2: fluorinated silicone modified flame retardant polyurethane hot melt adhesive is synthesized
By 15 parts of polytetrahydrofuran ether glycol PTMG, 15 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 30 parts of resistance
Combustible polyether glycol WANOL FR-130,15 parts 7380,30 parts of step 1 of crystalline polyester dihydric alcohol synthesize hydroxy-end capped
After phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object, 0.6 part of triethanolamine and the mixing of 0.6 part of irgasfos 168,130 are calorified
DEG C, water removal 2.5 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 70 DEG C, under nitrogen protection,
40 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), carry out polymerization reaction 4
Hour, sampling analysis polymerizate NCO% content reaches 2.5%, and viscosity reaches 6830 mPa.s, and 0.7 part silane coupled is added
Agent ND-42 obtains fluorinated silicone modified flame retardant polyurethane hot melt adhesive, is above mass fraction.Polytetrahydrofuran ether glycol PTMG's
Number-average molecular weight is 2000, and the number-average molecular weight of polyadipate -1,6- hexylene glycol esterdiol PHA is 1000, uses Brookfield
DV-C digital viscometer viscosity, test setting temperature are 100 DEG C.
Embodiment three
It is a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
15 parts of acrylic acid trifluoro ethyl ester TFMA, 10 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 40 parts of butyl acrylate BA and 15 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 90
In the toluene of part, 75 DEG C are controlled in, under nitrogen protection, 0.5 part of thermal initiator 4, bis- (the 4- cyano penta of 4'- azo are added
Alcohol), polymerization reaction 10 hours, after rotary evaporation removes toluene, obtain hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
That is P(TFMA-r-BAPDMS-r-BA-r-HMP), average each big point of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
1~2 hydroxy functional group is contained in subchain end, and the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is
28400；Methacryloxypropyl list block dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
Step 2: fluorinated silicone modified flame retardant polyurethane hot melt adhesive is synthesized
13 parts of polyoxypropyleneglycol PPG, 20 parts of polyethylene glycol adipate glycol PEA, 35 parts of flame retarding polyether is more
The hydroxy-end capped phosphor-containing flame-proof that first alcohol WANOL FR-312,20 parts of 7320,30 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After polyacrylic acid fluorine-silicon copolymer object, 0.3 part of 2,2- dimorpholine base Anaesthetie Ether and the mixing of 0.6 part of antioxidant 1010, heating
In 150 DEG C, water removal 3 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 80 DEG C, in nitrogen protection
Under, 35 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), polymerize anti-
It answers 5 hours, sampling analysis polymerizate NCO% content reaches 2.0%, and viscosity reaches 7960 mPa.s, and it is even that 1.4 parts of silane is added
Join agent ND-42, obtains fluorinated silicone modified flame retardant polyurethane hot melt adhesive, be above mass fraction.The number of polyoxypropyleneglycol PPG
Average molecular weight is 3000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is 1500, with Brookfield DV-C number
Word viscosity meter viscosity, test setting temperature are 100 DEG C.
Example IV
It is a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
18 parts of acrylic acid trifluoro ethyl ester TFMA, 15 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 40 parts of butyl acrylate (MA) and 20 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in
In 100 parts of toluene, 75 DEG C are controlled in, under nitrogen protection, 0.3 part of thermal initiator 4, bis- (the 4- cyano penta of 4'- azo are added
Alcohol), polymerization reaction 10 hours, after rotary evaporation removes toluene, obtain hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
That is P(TFMA-r-BAPDMS-r-BA-r-HMP), average each big point of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
1~2 hydroxy functional group is contained in subchain end, and the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is
38500；Methacryloxypropyl list block dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
Step 2: fluorinated silicone modified flame retardant polyurethane hot melt adhesive is synthesized
By 15 parts of polyoxypropyleneglycol PPG, 15 parts of polyadipate -1,4-butanediol esterdiol PBA, 40 parts fire-retardant poly-
Ethoxylated polyhydric alcohol WANOL FR-312,25 parts 7360,30 parts of step 1 of crystalline polyester dihydric alcohol synthesize hydroxy-end capped phosphorous
After flame-retardant polypropylene olefin(e) acid fluorine-silicon copolymer object, 0.5 part of triethanolamine and the mixing of 0.5 part of irgasfos 168,150 DEG C are calorified, is taken out
Vaccum dewatering 2 hours, until the water content of mixture is lower than 280ppm, cools down in 90 DEG C, under nitrogen protection, be added 40 parts
4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane -), carry out polymerization reaction 5 hours, take
Sample analysis polymerizate NCO% content reaches 2.1%, and viscosity reaches 12500 mPa.s, and 1.6 parts of silane coupling agent ND- is added
42, fluorinated silicone modified flame retardant polyurethane hot melt adhesive is obtained, is above mass fraction.The equal molecule of the number of polyoxypropyleneglycol PPG
Amount is 4000, and polyadipate -1,4-butanediol esterdiol PBA number-average molecular weight is 2000, with Brookfield DV-C number
Viscosity meter viscosity, test setting temperature are 100 DEG C.
Performance test
Universal method of the present invention referring to current hot melt adhesive, the ageing-resistant performance excellent flame that the four kinds of above embodiments are obtained
Damp solidifying polyurethane hot melt adhesive carries out melt viscosity, open hour, shore hardness, elongation at break, shear strength, oxygen index (OI)
With with the energy of resistance to acidity of oil index test.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, if
Set 100 DEG C.Open hour are tested referring to ASTM D4497-1994 (2004) method.Shore hardness is referring to GB-T2411-
2008 standards are tested.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is referring to GB/
T7124-2004 standard is tested.Oxygen index (OI) uses GB/T5454-1997 " textile combustion performance test-oxygen index method "
Measurement.The specific test method of chemical resistance index is to prepare sample with reference to test shear strength method, and it is small that sample places 72
When solidification after, sample is soaked in oleic acid (purity 98%) solution 24 hours, takes out sample, is placed in 85 DEG C and 85% relatively wet
It spends under environment, after carrying out aging 1000 hours, then carries out shear strength test.Water contact angle is marked with reference to GB/T 30693-2014
Standard is tested.All test data comparative situations are see the following table 1.
Each embodiment specific performance of table 1 tests control case
Can be seen that the fluorinated silicone modified flame retardant polyurethane hot melt adhesive that the present invention synthesizes from the data of table 1 has excellent waterproofness
Energy, chemical resistance and flame retardant property.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (4)
1. a kind of fluorinated silicone modified flame retardant polyurethane hot melt adhesive, it is characterised in that including 1~15 part of polyether Glycols, 1~30 part
Liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~30 part of crystalline polyester dihydric alcohol, 5~40 parts
Hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object, 10~50 parts of isocyanates, 0.1~1 part of catalyst, 0.1~1
The antioxidant and 0.1~2 part of silane coupling agent of part, are mass fraction above；The hydroxy-end capped phosphor-containing flame-proof polypropylene
The chemical structure of sour fluorine-silicon copolymer object is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-methacryloxypropyl list envelope
Hold dimethyl polysiloxane-it is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of butyl acrylate -) i.e. P
(TFMA-r-BAPDMS-r-BA-r-HMP), hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is averaged each macromolecular chain
1~2 hydroxy functional group is contained in end, and the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is 1000~
50000。
2. fluorinated silicone modified flame retardant polyurethane hot melt adhesive according to claim 1, it is characterised in that:
The polyether Glycols are polyoxypropyleneglycol PPG or polytetrahydrofuran ether two of the number-average molecular weight 500~4000
One or two kinds of any combination of alcohol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42.
3. a kind of preparation method of fluorinated silicone modified flame retardant polyurethane hot melt adhesive, it is characterised in that preparation step is as follows:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object
1~20 part of acrylic acid trifluoro ethyl ester TFMA, 1~20 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~50 part of butyl acrylate BA and 5~25 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP
It is dissolved in 50~100 parts of toluene, is controlled in 40~100 DEG C, under nitrogen protection, 0.1~3 part of thermal initiator 4 is added,
4'- azo is bis- (4- cyano amylalcohol), polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtains hydroxy-end capped phosphorous
Flame-retardant polypropylene olefin(e) acid fluorine-silicon copolymer object, the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object is 1000~
50000；
Step 2: fluorinated silicone modified flame retardant polyurethane hot melt adhesive is synthesized
1~15 part of polyether Glycols, 1~30 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~30
The hydroxy-end capped phosphor-containing flame-proof polyacrylic acid fluorine-silicon copolymer object of one synthesis of the step of crystalline polyester dihydric alcohol of part, 5~40 parts,
After 0.1~1 part of catalyst and the mixing of 0.1~1 part of antioxidant, 120~150 DEG C are calorified, it is small to vacuumize water removal about 1~3
When, until the water content of mixture is lower than 280ppm, cool down in 70~100 DEG C, under nitrogen protection, is added 10~50 parts
Isocyanates carries out polymerization reaction 1~5 hour, and sampling analysis polymerizate NCO% content reaches 1%~3%, tests at 100 DEG C
Viscosity reaches 3000~15000 mPa.s, and 0.1~2 part of silane coupling agent is added, and obtains fluorinated silicone modified flame retardant polyurethane hot melt
Glue is mass fraction above.
4. the preparation method of fluorinated silicone modified flame retardant polyurethane hot melt adhesive according to claim 3, it is characterised in that step 1
In methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
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| CN118421255A (en) * | 2024-07-05 | 2024-08-02 | 山东凯恩新材料科技有限公司 | Temperature-resistant high-viscosity adhesive and preparation method thereof |
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| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
| CN104262553A (en) * | 2014-09-19 | 2015-01-07 | 厦门大学 | Flame-retardant block copolymer containing nitrogen and phosphorus and preparation method thereof |
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| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
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| CN118421255A (en) * | 2024-07-05 | 2024-08-02 | 山东凯恩新材料科技有限公司 | Temperature-resistant high-viscosity adhesive and preparation method thereof |
| CN118421255B (en) * | 2024-07-05 | 2024-10-11 | 山东凯恩新材料科技有限公司 | Temperature-resistant high-viscosity adhesive and preparation method thereof |
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