CN117551415A - Polyurethane adhesive and preparation method thereof - Google Patents
Polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN117551415A CN117551415A CN202410026339.2A CN202410026339A CN117551415A CN 117551415 A CN117551415 A CN 117551415A CN 202410026339 A CN202410026339 A CN 202410026339A CN 117551415 A CN117551415 A CN 117551415A
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- polyol
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- isocyanate
- polyurethane adhesive
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 45
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004814 polyurethane Substances 0.000 title claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 79
- 150000003077 polyols Chemical class 0.000 claims abstract description 52
- -1 ether polyol Chemical class 0.000 claims abstract description 38
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 38
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- WKEDZWZMALHQCE-UHFFFAOYSA-N 2,4-diamino-5-methylbenzenethiol Chemical compound CC1=CC(S)=C(N)C=C1N WKEDZWZMALHQCE-UHFFFAOYSA-N 0.000 claims description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000004148 curcumin Substances 0.000 claims description 2
- 125000005266 diarylamine group Chemical group 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims 2
- HDMRYQCGZUYLJJ-UHFFFAOYSA-N 4-chloro-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(Cl)=C(N)C(SC)=C1N HDMRYQCGZUYLJJ-UHFFFAOYSA-N 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000008049 biological aging Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 150000008301 phosphite esters Chemical group 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 1
- 150000003672 ureas Chemical group 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
- C09J175/08—Polyurethanes from polyethers
-
- 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
- C08G18/4804—Two or more polyethers 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane adhesive and a preparation method thereof, wherein the polyurethane adhesive consists of a prepolymer A component and a curing agent B component, and the prepolymer A component comprises the following components in percentage by weight: 17.2% -28.5% of polyalcohol, 237.5% -70.0% of polyalcohol and 122.8% -34.0% of isocyanate; the curing agent B comprises the following components in percentage by weight: 354.1-59.6% of polyalcohol, 22.1-4.3% of isocyanate, 35.6-38.0% of chain extender, 2.1-2.7% of flatting agent and 0.6-0.9% of antioxidant; the polyol 1 is polytetrahydrofuran ether polyol with the number average molecular weight of 250-650; the polyol 2 is polytetrahydrofuran ether polyol with the number average molecular weight of 1000-2000; the polyol 3 is polytetrahydrofuran ether polyol with the number average molecular weight of 1000-2000. The polyurethane adhesive disclosed by the invention has higher tensile strength and elongation, and is more beneficial to packaging and bonding of complex electronic devices.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polyurethane adhesive and a preparation method thereof.
Background
The polyurethane adhesive is mainly prepared by reacting polyisocyanate with polyol and a chain extender, and the main chain of the polyurethane adhesive contains strong polar groups such as carbamate groups (-NHCOO-), isocyanate groups (-NCO), carbamide groups (-NHCONH-), and the like. In recent years, polyurethane adhesives develop rapidly, and are widely applied to bonding and sealing of aerospace and electronic devices due to the characteristics of wide adjustable range of performance, strong adaptability, wear resistance, oil resistance, biological aging resistance, strong operation manufacturability and the like.
In the field of sealing and bonding of electronic components, in order to ensure good packaging and bonding effects, the packaging layer is prevented from being damaged due to external force in the use process, and the packaging material needs to have good strength and elongation. In addition, for packaging and bonding of complex electronic devices, the materials are required to have good packaging performance and bonding performance, and the packaging is required to be carried out in a proper window, the packaging process comprises two stages of pouring and shaping, and the different stages have specific requirements on viscosity, wherein the initial viscosity of the packaging materials is usually required to be between 15000 mPa.s and 20000 mPa.s in the pouring stage, and defects easily occur in the pouring process due to the fact that the viscosity is too low or too high, so that the final packaging effect is influenced; the setting stage needs high viscosity increasing speed, and the viscosity within 2 hours is more than or equal to 20 thousand mPa.s so as to realize the rapid entering of the next working procedure.
CN113372872B provides a solvent-free polyurethane adhesive with high bonding fastness and a preparation method thereof. The adhesive is prepared from the component A and the component B, and the material has good adhesive property to a base material, but the viscosity of A, B components after being mixed for 3min is more than 23000 mPa.s, so that the adhesive is easy to cause defects when packaging complex devices.
Wang Xiaoqing (Wang Xiaoqing, etc. preparation and performance of reactive flame-retardant two-component polyurethane adhesive [ J ], polymer science and engineering, 3 months in 2014, 30, 3 rd, 149-152 pages) when the viscosity of the adhesive prepared by using polytetrahydrofuran glycol (PTMG 1000) as a raw material reaches 40000 mPa.s, 100 minutes is needed, which is not beneficial to curing and shaping of complex sample pieces; and the tensile strength of the adhesive is only 8.48MPa.
Luo Jiming (Luo Jiming et al, development of high-strength two-component polyurethane adhesive [ J ], bonding, volume 28, stage 1, pages 5-7 of 2007) two-component polyurethane adhesive prepared by using polycarbonate diol, ɛ -caprolactone-MOCA adduct and MDI as main materials, wherein the positioning time is 5min, the operation time is short, defects are easy to occur when packaging complex sample pieces, and the tensile strength is only 17.8MPa at most.
Therefore, the polyurethane adhesive with special viscosity requirement and high performance is suitable for pouring and packaging small components with complex structures and special tools, and is a technical problem to be solved in the prior art.
Disclosure of Invention
The invention provides a polyurethane adhesive and a preparation method thereof, which aim to solve the problems in the prior art. The polyurethane adhesive has the characteristics of high tensile strength and elongation, moderate viscosity in the packaging stage, convenience in operation and high viscosity increase in the later shaping stage, and is suitable for casting and packaging small components with complex structures and special tools.
The first aspect of the invention provides a polyurethane adhesive which consists of a prepolymer A component and a curing agent B component,
the prepolymer A component comprises the following components in percentage by weight:
polyol 1.2% -28.5%
Polyol 2.5% -70.0%
Isocyanate 1.8-34.0%
The curing agent B comprises the following components in percentage by weight:
polyol 3.1% -59.6%
2.1 to 4.3 percent of isocyanate
35.6 to 38.0 percent of chain extender
2.1 to 2.7 percent of leveling agent
0.6 to 0.9 percent of antioxidant
The polyol 1 is polytetrahydrofuran ether polyol with the number average molecular weight of 250-650; polytetrahydrofuran ether polyol with a number average molecular weight of 250 is preferred;
the polyol 2 is polytetrahydrofuran ether polyol with the number average molecular weight of 1000-2000; polytetrahydrofuran ether polyol with a number average molecular weight of 2000 is preferred;
the polyol 3 is polytetrahydrofuran ether polyol with the number average molecular weight of 1000-2000. Polytetrahydrofuran ether polyol with a number average molecular weight of 2000 is preferred;
the isocyanate 2 is toluene diisocyanate;
the preparation of the component A comprises the following steps:
(1) Adding polyol 1 and a part of isocyanate 1 into a reactor to react to obtain hydroxyl-terminated modified polytetrahydrofuran polyol;
(2) Adding polyol 2 and the rest of isocyanate 1 into the hydroxyl-terminated modified polytetrahydrofuran polyol obtained in the step (1) to react to obtain an-NCO-terminated prepolymer A component;
in the step (1), the molar ratio of-OH/-NCO of the polyol 1 to the isocyanate 1 is 2.0/1-2.3/1.
The isocyanate 1 is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), m-Xylylene Diisocyanate (XDI) and p-phenylene diisocyanate (PPDI). Toluene diisocyanate is preferred.
The chain extender is one or more of di-o-chlorodiphenylamine Methane (MOCA), dimethyl thiotoluenediamine (E-300), diethyl toluenediamine (E-100), 2, 4-diamino-3, 5-dimethyl thiochlorobenzene (TX-2), 2, 4-diamino-5-mercaptotoluene (TX-1), 4 '-methylene-bis (3-chloro-2, 6-diethylaniline) (MCDEA) and 4,4' -diamino diphenyl Methane (MDA). Di-o-chlorodiphenylamine Methane (MOCA) is preferred.
The leveling agent is one or more of polydimethylsiloxane, polymethylalkylsiloxane, organic modified polysiloxane and modified acrylic acid.
The antioxidant is one or more of secondary diarylamines, p-phenylenediamine, thioether and phosphite ester.
The second aspect of the invention provides a preparation method of a polyurethane adhesive, which comprises the following steps:
and (3) preparation of the component A:
(1) Adding polyol 1 and a part of isocyanate 1 into a reactor to react to obtain hydroxyl-terminated modified polytetrahydrofuran polyol;
(2) Adding polyol 2 and the rest of isocyanate 1 into the hydroxyl-terminated modified polytetrahydrofuran polyol obtained in the step (1) to react to obtain an-NCO-terminated prepolymer A component;
and (3) preparation of a component B:
(3) Adding polyol 3 and isocyanate 2 into a reactor, adding a leveling agent and an antioxidant after reaction, dehydrating, cooling to 70-90 ℃, adding a chain extender, and uniformly stirring to obtain a component B;
in the step (1), the molar ratio of-OH/-NCO of the polyol 1 to the isocyanate 1 is 2.0/1-2.3/1.
In the step (1), the reaction temperature is preferably 75-85 ℃, and the reaction time is preferably 2-3 h.
In the step (2), the NCO% content of the prepolymer A component is 4.9% -5.2%. Preferably, the polyol 2 is added and stirred uniformly, and then the rest isocyanate 1 is added; the reaction temperature is preferably 80-85 ℃, and the reaction time is preferably 2-3 h.
In the step (3), the molar ratio of-OH/-NCO of the polyol 3 to the isocyanate 2 is 2.0/1-2.3/1. The reaction temperature is preferably 80-85 ℃, and the reaction time is preferably 2-3 h.
Preferably, the-OH molar ratio of the polyol 2 to the polyol 1 is 0.45/1-1.2/1. Preferably, polyol 1, polyol 2 and polyol 3 are dehydrated prior to use, preferably at 100 to 110 ℃ to a moisture level of less than 300ppm.
The invention has the beneficial effects that the hydroxyl-terminated modified polytetrahydrofuran polyol obtained by reacting the polyol 1 with the number average molecular weight of 250-650 and the isocyanate 1 with the OH/NCO molar ratio of 2.0/1-2.3/1 reduces the problem of too high viscosity increase and no operation window caused by too high activity and fast reaction speed of the small molecular polytetrahydrofuran ether polyol in use, and meanwhile, the polyol 2 with the number average molecular weight of 1000-2000 and the rest of the isocyanate 1 are added for continuous reaction to finally obtain the-NCO-terminated A component. The adhesive can better meet the performance requirements of hardness, strength and the like, and meet the application requirements of adhesion and perfusion of complex electronic components.
Drawings
FIG. 1 is a graph showing the comparison of the previous viscosity changes of examples and comparative examples;
FIG. 2 is an enlarged view of embodiments 1-3 of FIG. 1;
FIG. 3 is a graph comparing the viscosity change at the end of examples and comparative examples;
fig. 4 is an enlarged view of example 1, example 2, and comparative example 2 in fig. 3.
Detailed Description
The present invention will be described in further detail with reference to examples, which are not intended to limit the scope of the invention.
Example 1
(1) And (3) preparation of a component A: adding 76.8g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 250 into a dry three-neck flask, adding 23.3g of toluene diisocyanate into the dry three-neck flask to react for 2.5 hours at the temperature of 80-85 ℃, adding 460.6g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 2000, adding 144.8g of toluene diisocyanate at the temperature of 50-60 ℃, reacting for 2 hours at the temperature of 80-85 ℃ to obtain a component A, and sealing and preserving for later use;
(2) And (3) preparation of a component B: adding 33.4g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 2000 into a three-neck flask, adding 1.26g of toluene diisocyanate, reacting for 2 hours at the temperature of 80-85 ℃, adding 1.2g of polydimethylsiloxane, 0.3g of diaryl secondary amine, dehydrating for 2 hours at the temperature of 110-120 ℃, cooling to 80 ℃, adding 20g of MOCA which is melted in advance, mixing and stirring for 1 hour at the temperature of 80-85 ℃ to obtain a curing agent B component, and sealing and preserving for later use;
(3) Preparation of the adhesive: the component A and the component B are mixed according to the proportion of 100/36.8 at room temperature, poured into a mold at 100 ℃, cured for 16 hours at 100-110 ℃ to obtain an adhesive sample, and the performance test is shown in the following table 1. Meanwhile, the viscosity increase of the A, B components mixed at room temperature is measured at 25 ℃, and the specific situation is shown in figures 1-4.
Example 2
(1) And (3) preparation of a component A: adding 74.18g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 250 into a dry three-neck flask, adding 25.82g of toluene diisocyanate into the dry three-neck flask to react for 2.5 hours at the temperature of 80-85 ℃, adding 460.6g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 2000, adding 144.8g of toluene diisocyanate at the temperature of 50-60 ℃, reacting for 2 hours at the temperature of 80-85 ℃ to obtain a component A, and sealing and preserving for later use;
(2) And (3) preparation of a component B: adding 33.4g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 2000 into a three-neck flask, adding 1.45g of toluene diisocyanate, reacting for 2 hours at the temperature of 80-85 ℃, adding 1.2. 1.2g polydimethylsiloxane, 0.3g of diaryl secondary amine, dehydrating for 2 hours at the temperature of 110-120 ℃, cooling to 80 ℃, adding 17.6g of TX-2 melted in advance, mixing and stirring for 1 hour at the temperature of 80-85 ℃ to obtain a curing agent B component, and sealing and preserving for later use;
(3) Preparation of the adhesive: the component A and the component B are mixed according to the proportion of 100/36.8 at room temperature, poured into a mold at 100 ℃, cured for 16 hours at 100-110 ℃ to obtain an adhesive sample, and the performance test is shown in the following table 1. Meanwhile, the viscosity increase of the A, B components mixed at room temperature is measured at 25 ℃, and the specific situation is shown in figures 1-4.
Example 3
(1) And (3) preparation of a component A: adding 85.67g of dehydrated polytetrahydrofuran ether polyol with molecular weight of 650 into a dry three-neck flask, adding 14.32g of diphenylmethane diisocyanate into the dry three-neck flask to react for 2.5 hours at 75-80 ℃, adding 180.39g of dehydrated polytetrahydrofuran ether polyol with molecular weight of 1000, adding 82.70g of toluene diisocyanate at 50-60 ℃, reacting for 2 hours at 80-85 ℃ to obtain a component A, and sealing and preserving for later use;
(2) And (3) preparation of a component B: adding 32.53g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 1000 into a three-neck flask, adding 2.46g of toluene diisocyanate, reacting for 2 hours at the temperature of 80-85 ℃, adding 1.2-g polydimethylsiloxane, 0.3g of diaryl secondary amine, dehydrating for 2 hours at the temperature of 110-120 ℃, cooling to 80 ℃, adding 20g of MOCA which is melted in advance, mixing and stirring for 1 hour at the temperature of 80-85 ℃ to obtain a curing agent B component, and sealing and preserving for later use;
(3) Preparation of the adhesive: the component A and the component B are mixed according to the proportion of 100/34 at room temperature, poured into a mold at 100 ℃, cured for 16 hours at 100-110 ℃ to obtain an adhesive sample, and the performance test is shown in the following table 1. Meanwhile, the viscosity increase of the A, B components mixed at room temperature is measured at 25 ℃, and the specific situation is shown in figures 1-3.
Comparative example 1
(1) And (3) preparation of the component A: heating and stirring 100g of polytetrahydrofuran ether polyol with molecular weight of 1000, heating to 100-110 ℃, vacuum dehydrating for 2h, cooling to 50 ℃, adding 31.20 toluene diisocyanate, reacting for 2h at 80-85 ℃, discharging, and sealing for preservation;
(2) The preparation of component B was the same as in example 1.
(3) Preparation of the adhesive: the component A and the component B are mixed according to the proportion of 100/36.8 at room temperature, poured into a mold at 100 ℃, cured for 16 hours at 100-110 ℃ to obtain the adhesive, and the performance test is shown in the following table 1. The viscosity increase of the A, B component mixed at room temperature was measured at 25℃and is shown in FIGS. 1 and 3.
Comparative example 2
(1) And (3) preparation of the component A: heating and stirring 76.8g of polytetrahydrofuran ether polyol with the molecular weight of 250 and 460.6g of polytetrahydrofuran ether polyol with the molecular weight of 2000, heating to 100-110 ℃, dehydrating in vacuum for 2h, cooling to 50 ℃, adding 168.1g of toluene diisocyanate, reacting for 2h at 80-85 ℃, discharging, and sealing for storage;
(2) The preparation of component B was the same as in example 1;
(3) Preparation of the adhesive: the component A and the component B are mixed according to the proportion of 100/36.8 at room temperature, poured into a mold at 100 ℃, cured for 16 hours at 100-110 ℃ to obtain the adhesive, and the performance test is shown in the following table 1. Meanwhile, the viscosity increase of the A, B components mixed at room temperature is measured at 25 ℃, and the specific conditions are shown in figures 1 and 3-4.
Comparative example 3
(1) And (3) preparation of a component A: 68.30g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 250 is added into a dry three-neck flask, 31.69g of toluene diisocyanate (-OH/-NCO molar ratio is 1.5/1) is added into the dry three-neck flask, the viscosity is excessive after the reaction is carried out for 2.5 hours at the temperature of 80-85 ℃, and the next experiment can not be carried out in a gel-like state.
Comparative example 4
(1) And (3) preparation of a component A: adding 81.17g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 250 into a dry three-neck flask, adding 18.83g of toluene diisocyanate (-OH/-NCO molar ratio of 3.0/1) into the dry three-neck flask, reacting for 2.5 hours at 80-85 ℃, adding 176.48g of dehydrated polytetrahydrofuran ether polyol with the molecular weight of 2000, adding 86.45g of toluene diisocyanate at 50-60 ℃, reacting for 2 hours at 80-85 ℃ to obtain a component A, and sealing and preserving for later use;
(2) The preparation of component B was the same as in example 1;
(3) Preparation of the adhesive: the component A and the component B are mixed according to the proportion of 100/36.8 at room temperature, poured into a mold at 100 ℃, cured for 16 hours at 100-110 ℃ to obtain an adhesive sample, and the performance test is shown in the following table 1. The viscosity increase of the A, B component mixed at room temperature was measured at 25℃and is shown in FIGS. 1 and 3.
The properties of the materials obtained in the examples and comparative examples are shown in Table 1.
Table 1 properties of materials obtained in examples and comparative examples
As can be seen from the data in table 1, the examples have higher tensile strength and elongation. Meanwhile, as can be seen from the viscosity change curves in fig. 1 to 4, the viscosity of comparative example 1 increases slowly, the initial viscosity at the early stage is less than 15000 mpa·s, the material leakage is easy to occur in the pouring stage, the viscosity at the later stage is about 100000 mpa·s, and the package cannot be fixed. Comparative example 2 although the later viscosity increase tendency was close to that of examples 1 and 2, the earlier viscosity was large, the initial viscosity was > 30000mpa·s, and filling defects were liable to occur at the time of the packaging operation. While comparative example 4 has a high viscosity, is difficult to operate in the early stage, and is prone to filling defects in the later stage. Compared with the prior art, the embodiment has small early-stage viscosity, is more beneficial to the operation of the packaging stage of the complex sample, has quicker later-stage viscosity increase, is more beneficial to the later-stage shaping of the complex sample, and meets the filling and packaging requirements of the complex tool. Therefore, the polyurethane adhesive is more beneficial to the adhesion and the filling of small components with complex structures.
Claims (9)
1. A polyurethane adhesive comprises a prepolymer A component and a curing agent B component,
the prepolymer A component comprises the following components in percentage by weight:
polyol 1.2% -28.5%
Polyol 2.5% -70.0%
Isocyanate 1.8-34.0%
The curing agent B comprises the following components in percentage by weight:
polyol 3.1% -59.6%
2.1 to 4.3 percent of isocyanate
35.6 to 38.0 percent of chain extender
2.1 to 2.7 percent of leveling agent
0.6 to 0.9 percent of antioxidant
The polyol 1 is polytetrahydrofuran ether polyol with the number average molecular weight of 250-650;
the polyol 2 is polytetrahydrofuran ether polyol with the number average molecular weight of 1000-2000;
the polyol 3 is polytetrahydrofuran ether polyol with the number average molecular weight of 1000-2000;
the isocyanate 2 is toluene diisocyanate;
the preparation of the component A comprises the following steps:
(1) Adding polyol 1 and a part of isocyanate 1 into a reactor to react to obtain hydroxyl-terminated modified polytetrahydrofuran polyol;
(2) Adding polyol 2 and the rest of isocyanate 1 into the hydroxyl-terminated modified polytetrahydrofuran polyol obtained in the step (1) to react to obtain an-NCO-terminated prepolymer A component;
in the step (1), the molar ratio of-OH/-NCO of the polyol 1 to the isocyanate 1 is 2.0/1-2.3/1.
2. The polyurethane adhesive of claim 1, wherein the isocyanate 1 is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophthalene diisocyanate (XDI), and terephthalyl diisocyanate (PPDI).
3. The polyurethane adhesive of claim 1, wherein the chain extender is one or more of di-o-chlorodiphenylamine Methane (MOCA), dimethylthiotoluenediamine (E-300), diethyltoluenediamine (E-100), 2, 4-diamino-3, 5-dimethylthiochlorobenzene (TX-2), 2, 4-diamino-5-mercaptotoluene (TX-1), 4 '-methylene-bis (3-chloro-2, 6-diethylaniline) (MCDEA), 4' -diaminodiphenylmethane (MDA).
4. The polyurethane adhesive of claim 1, wherein the leveling agent is one or more of polydimethylsiloxane, polymethylalkylsiloxane, organomodified polysiloxane, and modified acrylic acid.
5. The polyurethane adhesive of claim 1, wherein the antioxidant is one or more of a secondary diarylamine, a para-phenylenediamine, a thioether, and a phosphite.
6. A method for preparing the polyurethane adhesive according to any one of claims 1 to 5, comprising the following steps:
and (3) preparation of the component A:
(1) Adding polyol 1 and a part of isocyanate 1 into a reactor to react to obtain hydroxyl-terminated modified polytetrahydrofuran polyol;
(2) Adding polyol 2 and the rest of isocyanate 1 into the hydroxyl-terminated modified polytetrahydrofuran polyol obtained in the step (1) to react to obtain an-NCO-terminated prepolymer A component;
and (3) preparation of a component B:
(3) Adding polyol 3 and isocyanate 2 into a reactor, adding a leveling agent and an antioxidant after reaction, dehydrating, cooling to 70-90 ℃, adding a chain extender, and uniformly stirring to obtain a component B;
in the step (1), the molar ratio of-OH/-NCO of the polyol 1 to the isocyanate 1 is 2.0/1-2.3/1.
7. The method for preparing a polyurethane adhesive according to claim 6, wherein in the step (2), the NCO% content of the prepolymer A component is 4.9% -5.2%.
8. The method for preparing a polyurethane adhesive according to claim 6, wherein in the step (3), the molar ratio of-OH/-NCO of the polyol 3 to the isocyanate 2 is 2.0/1 to 2.3/1.
9. The method for preparing a polyurethane adhesive according to claim 6, wherein the-OH molar ratio of the polyol 2 to the polyol 1 is 0.45/1 to 1.2/1.
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