CN116218451A - Polyurethane structural adhesive for bonding automobile composite material - Google Patents
Polyurethane structural adhesive for bonding automobile composite material Download PDFInfo
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- CN116218451A CN116218451A CN202211643294.0A CN202211643294A CN116218451A CN 116218451 A CN116218451 A CN 116218451A CN 202211643294 A CN202211643294 A CN 202211643294A CN 116218451 A CN116218451 A CN 116218451A
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- polyester polyol
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 31
- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 21
- 239000004814 polyurethane Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 27
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 11
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 239000000539 dimer Substances 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 9
- 239000002516 radical scavenger Substances 0.000 claims abstract description 9
- 239000004526 silane-modified polyether Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OYBMVMAXKOGYDC-UHFFFAOYSA-N CTPB Chemical group CCCCCCCCCCCCCCCC1=CC=CC(OCC)=C1C(=O)NC1=CC=C(Cl)C(C(F)(F)F)=C1 OYBMVMAXKOGYDC-UHFFFAOYSA-N 0.000 claims description 6
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 3
- QIIDATRCGITYRZ-UHFFFAOYSA-N Catalpol Natural products OCC1OC(OC2OC=CC3C(O)C(=C(CO)C23)O)C(O)C(O)C1O QIIDATRCGITYRZ-UHFFFAOYSA-N 0.000 claims 1
- LHDWRKICQLTVDL-PZYDOOQISA-N catalpol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@@H]2[C@@]3(CO)O[C@H]3[C@@H](O)[C@@H]2C=CO1 LHDWRKICQLTVDL-PZYDOOQISA-N 0.000 claims 1
- UXSACQOOWZMGSE-UHFFFAOYSA-N catalposide Natural products OC1C(O)C(O)C(CO)OC1OC1C2C3(CO)OC3C(OC(=O)C=3C=CC(O)=CC=3)C2C=CO1 UXSACQOOWZMGSE-UHFFFAOYSA-N 0.000 claims 1
- LHDWRKICQLTVDL-UHFFFAOYSA-N methyl iridoid glycoside Natural products OC1C(O)C(O)C(CO)OC1OC1C2C3(CO)OC3C(O)C2C=CO1 LHDWRKICQLTVDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 150000004756 silanes Polymers 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 229920002379 silicone rubber Polymers 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to polyurethane structural adhesive for bonding an automobile composite material, which consists of a component A and a component B, wherein the component A comprises the following components: modified polyester polyol, polyether modified silane, hydroxyl-terminated polyisoprene, carboxyl-terminated polybutadiene, a dispersing agent, carbon black, a catalyst, a light calcium filler, a heavy calcium filler, a water scavenger and gas silicon; the component B comprises: dimer acid polyester polyol, hydroxyl-terminated polybutadiene, isocyanate, dispersant, silica micropowder filler and titanium dioxide. The structural adhesive prepared by the invention has extremely low modulus, is close to silicon rubber at normal temperature, has low viscosity and good touch change, is favorable for sizing in various complex environments, and has excellent bonding performance to various base materials and excellent weather-resistant and shock-resistant effects. The outstanding characteristics are high peel strength, obvious price advantage and high economic benefit.
Description
Technical Field
The invention relates to the field of polyurethane structural adhesives, in particular to a polyurethane structural adhesive for bonding an automobile diversified composite material structure.
Background
Along with the increasing shortage of international situation, the global energy strategic resource price is high, the energy problem of China, which is a petroleum import country, is not solved all the time, the domestic crude oil price is continuously increased, the use cost of the fuel oil automobile is increased, and the transportation cost is increased to influence the price of the materials, so that the people are directly related to the clothing and eating residence.
Under the background, new energy automobiles are generated, the national new energy automobiles are exploded, trucks, buses and buses face a new iteration, and the future development prospect of the automobile industry is wide
For the whole automobile, composite materials such as automobile decorative strips, interior floors and the like are various in structure, various in material types, complex in bonding environment and large in demand, and an adhesive capable of meeting various different application scenes is needed.
Disclosure of Invention
In order to solve the problems, the polyurethane structural adhesive prepared by the invention can effectively meet the requirement of bonding of automobile composite materials, has the characteristics of good manufacturability and diversified designs, and plays the roles of high stripping, low modulus, high reliability and shock resistance by introducing rubber resin.
The technical scheme for solving the technical problems is as follows: a polyurethane structural adhesive for bonding an automobile composite material comprises a component A and a component B, wherein the weight ratio of the component A to the component B is (1-3) 1, and the component A comprises the following components in parts by weight: 12-16 parts of modified polyester polyol, 14-24 parts of polyether modified silane, 5-10 parts of hydroxyl-terminated polyisoprene, 3-8 parts of carboxyl-terminated polybutadiene, 0.3-1.2 parts of dispersing agent, 0.1-0.3 part of carbon black, 0.1-0.5 part of catalyst, 6-11 parts of light calcium filler, 6-10 parts of heavy calcium filler, 1-4 parts of water scavenger and 1-3 parts of gas silicon; the component B comprises: 15-25 parts of dimer acid polyester polyol, 10-15 parts of hydroxyl-terminated polybutadiene, 15-25 parts of isocyanate, 0.1-0.4 part of dispersing agent, 15-20 parts of silica micropowder filler and 0.1-0.3 part of titanium dioxide.
Further, the modified polyester polyol has a molecular weight of 470g/mol, a functionality of 2, and a hydroxyl value of 230 to 250 mgKOH.g -1 The preparation method comprises the following steps:
the basic reaction equation is shown below:
(1) 100g of 2, 5-furandicarboxylic acid (FDCA) and 160g of diethylene glycol (DEG) were put into a four-necked flask, a thermometer and a condenser were inserted, and the flask was filled with nitrogen gas and stirred;
(2) Heating the oil bath pot to set the temperature at 140 ℃, controlling the temperature of a reaction system at 135 ℃, separating water generated by the esterification reaction at a position through a condensing tube, and reacting for 1h;
(3) And (3) heating to 180 ℃ for continuous reaction, observing that condensed water is not generated basically, heating to 270 ℃ and vacuumizing, and separating the redundant diethylene glycol DEG and water in the system completely to obtain the required modified polyester polyol.
Further, the polyether modified silane has a molecular weight of 2000, preferably of L1160, a molecular weight of 3500, preferably of ziplon chemical industry limited, and a molecular weight of 3000, preferably of carboxyl terminated polybutadiene, preferably CTPB, a pharmaceutical industry limited, wuhanana white. The introduction of the rubber resin can improve the flexibility and the tensile strength of polyurethane at low temperature to a limited extent, and can reduce the modulus of products, so that the polyurethane adhesive has part of the performance of rubber.
Further, the dispersing agent is preferably a Pick aid BYK-W966, the carbon black is preferably Tianjin Huaran chemical engineering Co., ltd, the catalyst is an organic bismuth catalyst, and the carbon black is preferably WCAT-NS01 of Guangzhou Yourun chemical Co., ltd.
Further, the light calcium filler is 1250 mesh, preferably JZ-38, a chemical industry Co., ltd. In Shandong, and the heavy calcium filler is 1250 mesh, preferably CHANGSEN-042, a mineral products Co., changsen, ministry of Pacific, lingShang. The reasonable collocation of the light calcium carbonate and the heavy calcium carbonate not only can reinforce the system to a certain extent, but also can effectively control the viscosity and thixotropic property of the product, so that the light calcium carbonate and the heavy calcium carbonate can be better suitable for application scenes.
Further, the water scavenger is 3A molecular sieve activated powder, preferably Australian catalytic material (Dalian) Co., ltd. AS-103, and the gas silicon is preferably Hubei Hui Fu nano material Co., ltd. HB-132.
Further, the dimer acid polyester polyol has a molecular weight of 2000, preferably T-568, german winning chemical, and the hydroxyl-terminated polybutadiene has a molecular weight of 3600, preferably HT.
Further, the isocyanate is liquefied MDI, preferably Wanhua chemical YHMDI, the dispersant is preferably a Pick aid BYK-W966, and the silica powder filler is 1250 meshes, preferably MJ-2000, a crystal silicon material company of Lian Yungang vast, and the titanium dioxide is preferably HA100, a Nanyang Hengxiang chemical product company.
Furthermore, the adhesive force of the glue to various base materials, especially the adhesion to aluminum materials, can be effectively improved by introducing carboxyl-terminated polybutadiene, the curing state of the polyurethane glue can be changed by introducing carboxyl-terminated polyisoprene and hydroxyl-terminated polybutadiene, a rubber state is achieved, the excellent effect of low modulus and high stripping is achieved, meanwhile, the weather resistance of polyurethane is greatly improved by introducing rubber resin, the integral surface energy of the glue can be reduced by introducing polyether modified organic silicon resin, the glue has good adhesion to various composite materials such as FR4 boards and ABS, the weather resistance and the water resistance are greatly improved, and the glue performance is optimal by mutually matching.
The beneficial effects of the invention are as follows: the structural adhesive prepared by the invention has extremely low modulus, is close to silicon rubber at normal temperature, has low viscosity and good touch change, is favorable for sizing in various complex environments, and has excellent bonding performance to various base materials and excellent weather-resistant and shock-resistant effects. The outstanding characteristics are high peel strength, obvious price advantage and high economic benefit.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
The modified polyester polyol synthesis step comprises:
1) 100g of 2, 5-furandicarboxylic acid (FDCA) (Aba Ding Shiji) and 160g of diethylene glycol (DEG) (Aba Ding Shiji) were put into a four-necked flask, a thermometer and a condenser were inserted, and the flask was filled with nitrogen gas and stirred;
(2) Heating the oil bath pot to set the temperature at 140 ℃, controlling the temperature of a reaction system at 135 ℃, separating water generated by the esterification reaction at a position through a condensing tube, and reacting for 1h;
(3) Heating to 180 ℃ for continuous reaction, observing that the system basically generates no condensed water, heating to 270 ℃ and vacuumizing, and separating excessive DEG and water in the system completely to obtain the required polyester polyol. The molecular weight of the modified polyester polyol is 470, and the hydroxyl value is 230-250mgKOH g –1 。
Example 1
13.0g of modified polyester polyol, 1160.0 g of polyether modified silane L, 6.0g of hydroxyl-terminated polyisoprene, 5.0g of carboxyl-terminated polybutadiene CTPB, 0.4g of dispersant BYK-W966 and 0.3g of carbon black N966 are added, uniformly mixed, and then 0.2g of catalyst WCAT-NS01, 389.0g of light calcium filler JZ-389.0g, 10.0g of heavy calcium filler CHANGSEN-042, 3.0g of water scavenger AS-103, and HB-1321.0g of gas silicon are added, and uniformly mixed by deaeration to obtain the A component structural adhesive; and the component B comprises the following components: firstly, prepolymerizing 17.0g of dimer acid polyester polyol T-568 g, 12.0g of hydroxyl-terminated polybutadiene HT and 25.0g of isocyanate YHMDI at 80 ℃ for 2 hours, adding 0.1g of dispersant BYK-W966 and 20.0g of silica powder filler MJ-2000.0 g after the temperature is reduced to normal temperature, and uniformly mixing the components with titanium dioxide HA-100.3 g in a defoaming way to obtain the component B. When in use, the AB component is uniformly mixed according to the ratio of 2:1, and then the mixture is filled on a workpiece to be injected, and the mixture is cured at normal temperature or is heated and cured at the temperature below 80 ℃.
Example 2
13.5g of modified polyester polyol, 1160.0 g of polyether modified silane L1160.0 g, 6.0g of hydroxyl-terminated polyisoprene, 5.0g of carboxyl-terminated polybutadiene CTPB, 0.5g of dispersant BYK-W966 and 0.4g of carbon black N966 are added, uniformly mixed, and then 0.2g of catalyst WCAT-NS01, 3810.0g of light calcium filler JZ-3810.0g, 9.0g of heavy calcium filler CHANGSEN-042, 3.0g of water scavenger AS-103, and HB-1321.0g of gas silicon are added, and uniformly mixed by deaeration to obtain the A component structural adhesive; and the component B comprises the following components: firstly, prepolymerizing 17.0g of dimer acid polyester polyol T-568, 12.0g of hydroxyl-terminated polybutadiene HT and 26.0g of isocyanate YHMDI at 80 ℃ for 2 hours, after the temperature is reduced to normal temperature, adding 0.1g of dispersant BYK-W966 and 21.0g of silica powder filler MJ-2000, and uniformly mixing the components by defoaming to obtain the component B. When in use, the AB component is uniformly mixed according to the ratio of 2:1, and then the mixture is filled on a workpiece to be injected, and the mixture is cured at normal temperature or is heated and cured at the temperature below 80 ℃.
Example 3
13.0g of modified polyester polyol, 1160.0 g of polyether modified silane L, 6.0g of hydroxyl-terminated polyisoprene, 4.0g of carboxyl-terminated polybutadiene CTPB, 0.5g of dispersant BYK-W966 and 0.4g of carbon black N966 are added, uniformly mixed, and then 0.2g of catalyst WCAT-NS01, 388.0g of light calcium filler JZ-388.0g, 11.0g of heavy calcium filler CHANGSEN-042, 3.0g of water scavenger AS-103, and HB-1321.0g of gas silicon are added, and uniformly mixed by deaeration to obtain the A component structural adhesive; and the component B comprises the following components: firstly, prepolymerizing 17.0g of dimer acid polyester polyol T-568, 12.0g of hydroxyl-terminated polybutadiene HT and 26.0g of isocyanate YHMDI at 80 ℃ for 2 hours, after the temperature is reduced to normal temperature, adding 0.1g of dispersant BYK-W966 and 21.0g of silica powder filler MJ-2000, and uniformly mixing the components by defoaming to obtain the component B. When in use, the AB component is uniformly mixed according to the ratio of 2:1, and then the mixture is filled on a workpiece to be injected, and the mixture is cured at normal temperature or is heated and cured at the temperature below 80 ℃.
Comparative example 1
13.0g of castor oil polyol H368 (Eyew oil Co., ltd.), 15.0g of polyether modified silane L1160.0 g of hydroxyl-terminated polyisoprene 6g, 5g of carboxyl-terminated polybutadiene CTPB, 0.4g of dispersant BYK-W966 and 0.3g of carbon black N966 are added and uniformly mixed, and then the catalyst WCAT-NS010.2g, light calcium filler JZ-38 g, heavy calcium filler CHANGSEN-042 10g, water scavenger AS-1033g and gas silicon HB-132 g are added and uniformly mixed to obtain the A component structural adhesive; and the component B comprises the following components: firstly, prepolymerizing 17g of dimer acid polyester polyol T-568 g, 12g of hydroxyl-terminated polybutadiene HT and 25g of isocyanate YHMDI at 80 ℃ for 2 hours, after the temperature is reduced to normal temperature, adding 0.1g of dispersant BYK-W966 and 20g of silica powder filler MJ-2000 g, and uniformly defoaming and mixing the mixture to obtain the component B. When in use, the AB component is uniformly mixed according to the ratio of 2:1, and then the mixture is filled on a workpiece to be injected, and the mixture is cured at normal temperature or is heated and cured at the temperature below 80 ℃.
The structural adhesives obtained in examples 1 to 3 and comparative example 1 were tested, and comparative tests were repeated; the heat curing conditions were 80℃and 4h heat curing. The results are shown in Table 1.
TABLE 1 test of structural adhesive Properties of examples 1-3
Through the comparison test, compared with the commercial castor oil polyol, the prepared polyurethane structural adhesive has lower modulus, better compatibility when being matched with rubber resin, effectively improves the adhesive force to various base materials, obviously improves the peeling strength and obviously improves the breaking elongation.
Compared with the main polyurethane structural adhesive in the market, the invention introduces a large amount of rubber resin and polyether modified silicone resin, greatly reduces the modulus of the adhesive, ensures that the adhesive has higher shock resistance and weather resistance, and has high adhesiveness to various composite materials and obvious improvement of peel strength. The application is wider, and the glue with higher coverage is provided.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The polyurethane structural adhesive for bonding the automobile composite material is characterized by comprising a component A and a component B, wherein the weight ratio of the component A to the component B is (1-3): 1, and the component A comprises the following components in parts by weight: 12-16 parts of modified polyester polyol, 14-24 parts of polyether modified silane, 5-10 parts of hydroxyl-terminated polyisoprene, 3-8 parts of carboxyl-terminated polybutadiene, 0.3-1.2 parts of dispersing agent, 0.1-0.3 part of carbon black, 0.1-0.5 part of catalyst, 6-11 parts of light calcium filler, 6-10 parts of heavy calcium filler, 1-4 parts of water scavenger and 1-3 parts of gas silicon; the component B comprises: 15-25 parts of dimer acid polyester polyol, 10-15 parts of hydroxyl-terminated polybutadiene, 15-25 parts of isocyanate, 0.1-0.4 part of dispersing agent, 15-20 parts of silica micropowder filler and 0.1-0.3 part of titanium dioxide;
the molecular weight of the modified polyester polyol is 470g/mol, the functionality is 2, and the hydroxyl value is 230
-250mgKOH·g -1 。
2. The polyurethane construction adhesive for bonding an automobile composite material according to claim 1, wherein the modified polyester polyol is prepared by the steps of:
(1) 100g of 2, 5-furandicarboxylic acid and 160g of diethylene glycol are added into a four-necked flask, a thermometer and a condenser tube are inserted, and nitrogen is filled for stirring;
(2) Heating the oil bath pot to set the temperature at 140 ℃, controlling the temperature of a reaction system at 135 ℃, separating water generated by the esterification reaction at a position through a condensing tube, and reacting for 1h;
(3) Heating to 180 ℃ for continuous reaction, observing that the system basically generates no condensed water, heating to 270 ℃ and vacuumizing, and separating the redundant diethylene glycol and water in the system completely to obtain the required modified polyester polyol.
3. The polyurethane construction adhesive for bonding an automotive composite material according to claim 1, wherein the polyether-modified silane has a molecular weight of 2000 and is L1160, a michaux company; the molecular weight of the hydroxyl-terminated polyisoprene is 3500, which is a catalpol chemical company; the molecular weight of the carboxyl-terminated polybutadiene is 3000, and the carboxyl-terminated polybutadiene is CTPB of the pharmaceutical chemical industry Co., ltd.
4. The polyurethane structural adhesive for bonding an automobile composite material according to claim 1, wherein the dispersing agent is a Pick aid BYK-W966, the catalyst is an organic bismuth catalyst, and the dispersing agent is WCAT-NS01 of Guangzhou excellent wetting chemistry Co.
5. The polyurethane structural adhesive for bonding an automobile composite material according to claim 1, wherein the light calcium filler is 1250 mesh and is JZ-38 of shandong chemical industry limited; the heavy calcium filler is 1250 meshes and is CHANGSEN-042 of Changsen mineral products limited in Ministry of life county.
6. The polyurethane structural adhesive for bonding an automobile composite material according to claim 1, wherein the water scavenger is 3A molecular sieve activated powder, which is aus catalytic material (da even) AS-103; the gas silicon is HB-132 of Hubei Hui Fu nanomaterial Co., ltd.
7. The polyurethane construction adhesive for bonding an automotive composite material according to claim 1, wherein the dimer acid polyester polyol has a molecular weight of 2000, which is a german win-creation chemical T-568; the molecular weight of the hydroxyl-terminated polybutadiene is 3600, which is the German winning chemical HT.
8. The polyurethane structural adhesive for bonding an automotive composite material according to claim 1, wherein the isocyanate is liquefied MDI; the dispersing agent is a Pick aid BYK-W966; the silica powder filler is 1250 meshes and is MJ-2000 of a crystal silicon material limited company of Lianyuangang vast; the titanium dioxide is HA100 of Nanyang constant-flying chemical products.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652937A (en) * | 2017-11-06 | 2018-02-02 | 烟台德邦科技有限公司 | Preparation method of polyurethane hot melt adhesive capable of being bonded with low surface energy material |
| CN111247223A (en) * | 2017-10-25 | 2020-06-05 | 汉高股份有限及两合公司 | Polyester polyol-based binders based on furan dicarboxylic acids obtained from renewable raw materials |
| CN111303818A (en) * | 2020-04-13 | 2020-06-19 | 山东誉中新材料股份有限公司 | Polyurethane foaming adhesive |
| CN111349417A (en) * | 2020-05-07 | 2020-06-30 | 北京天山新材料技术有限公司 | Polyurethane adhesive composition and polyurethane adhesive |
| CN111808570A (en) * | 2020-08-27 | 2020-10-23 | 格丽泰新材料科技（苏州）有限公司 | Double-component polyurethane adhesive and application thereof |
| CN113637448A (en) * | 2021-08-17 | 2021-11-12 | 湖北回天新材料股份有限公司 | Single-component polyurethane corner-combining adhesive and preparation method thereof |
| CN114316880A (en) * | 2021-12-29 | 2022-04-12 | 烟台德邦科技股份有限公司 | Low-density high-heat-conductivity polyurethane structural adhesive |
| CN115058224A (en) * | 2022-06-27 | 2022-09-16 | 浙江华峰合成树脂有限公司 | Reactive polyurethane hot melt adhesive |
-
2022
- 2022-12-20 CN CN202211643294.0A patent/CN116218451A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111247223A (en) * | 2017-10-25 | 2020-06-05 | 汉高股份有限及两合公司 | Polyester polyol-based binders based on furan dicarboxylic acids obtained from renewable raw materials |
| CN107652937A (en) * | 2017-11-06 | 2018-02-02 | 烟台德邦科技有限公司 | Preparation method of polyurethane hot melt adhesive capable of being bonded with low surface energy material |
| CN111303818A (en) * | 2020-04-13 | 2020-06-19 | 山东誉中新材料股份有限公司 | Polyurethane foaming adhesive |
| CN111349417A (en) * | 2020-05-07 | 2020-06-30 | 北京天山新材料技术有限公司 | Polyurethane adhesive composition and polyurethane adhesive |
| CN111808570A (en) * | 2020-08-27 | 2020-10-23 | 格丽泰新材料科技（苏州）有限公司 | Double-component polyurethane adhesive and application thereof |
| CN113637448A (en) * | 2021-08-17 | 2021-11-12 | 湖北回天新材料股份有限公司 | Single-component polyurethane corner-combining adhesive and preparation method thereof |
| CN114316880A (en) * | 2021-12-29 | 2022-04-12 | 烟台德邦科技股份有限公司 | Low-density high-heat-conductivity polyurethane structural adhesive |
| CN115058224A (en) * | 2022-06-27 | 2022-09-16 | 浙江华峰合成树脂有限公司 | Reactive polyurethane hot melt adhesive |
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