CN115746777A - Flexible single-component reaction type cold-pasting adhesive and preparation method and application thereof - Google Patents
Flexible single-component reaction type cold-pasting adhesive and preparation method and application thereof Download PDFInfo
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- CN115746777A CN115746777A CN202211418335.6A CN202211418335A CN115746777A CN 115746777 A CN115746777 A CN 115746777A CN 202211418335 A CN202211418335 A CN 202211418335A CN 115746777 A CN115746777 A CN 115746777A
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- isocyanate
- diisocyanate
- diphenylmethane diisocyanate
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- 239000000853 adhesive Substances 0.000 title claims abstract description 62
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 62
- 238000006757 chemical reactions by type Methods 0.000 title claims description 50
- 238000002360 preparation method Methods 0.000 title description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 104
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 104
- 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 abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000004744 fabric Substances 0.000 claims abstract description 6
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 5
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 87
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 49
- 125000005442 diisocyanate group Chemical group 0.000 claims description 42
- 239000002518 antifoaming agent Substances 0.000 claims description 38
- 239000007822 coupling agent Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 30
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 30
- 239000002318 adhesion promoter Substances 0.000 claims description 29
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 29
- 239000003208 petroleum Substances 0.000 claims description 27
- 238000011049 filling Methods 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 238000005070 sampling Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 18
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 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 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- -1 tert-butyl phenolic resin Chemical compound 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 239000011505 plaster Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 9
- 238000007639 printing Methods 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007965 rubber solvent Substances 0.000 description 2
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- 238000001035 drying Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
A flexible single-component reactive cold-applied adhesive, comprising: the cold-patch adhesive is prepared from a polyurethane elastomer polymer (TPU), tackifying resin and isocyanate; the isocyanate is a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate. The mass ratio of the 2,3 '-diphenylmethane diisocyanate to the 4,4' -diphenylmethane diisocyanate is controlled to be 60-98, compared with single diphenylmethane diisocyanate, the mixture of the 2,3 '-diphenylmethane diisocyanate and the 4,4' -diphenylmethane diisocyanate has better adhesive force to silk fabrics or synthetic fibers and metal frames, and simultaneously has better high temperature resistance and water resistance, and can be quickly cured and dried in a short time, and the strength after curing can meet the daily use requirement.
Description
Technical Field
The invention relates to a cold adhesive and a preparation method thereof, in particular to a flexible single-component reaction type cold adhesive and a preparation method thereof, and belongs to the technical field of adhesive preparation.
Background
The screen printing is one of four common printing modes, and during printing, ink is transferred to a printing stock through meshes of an image-text part by extrusion of a scraper plate to form images and texts same as those of an original manuscript. The screen printing equipment is simple, the operation is convenient, the printing and the plate making are simple, the cost is low, the adaptability is strong, the printing can be carried out on the printing stocks with curved surfaces, spherical surfaces and concave-convex surfaces, the screen printing is accepted by more and more industries, and the application is wide. Such as circuit board of domestic electric appliance, pattern on the textile, characters on the panel of refrigerator, TV set and washing machine, decoration on the ceramic, glass and wall and floor tiles, various commercial advertisement such as electric appliance, package, net-printed high-grade packing box in package decoration industry, ultra-large external package and product appearance decoration.
Screen printing consists of five major elements, namely a screen printing plate, a squeegee, ink, a printing table, and a substrate. In the manufacturing process of the screen printing plate, a screen made of silk fabric or synthetic fiber fabric needs to be adhered to a screen frame (generally a metal screen frame), and is required to be cured and dried quickly within 30min and pass UV, high temperature and water boiling tests.
At present, glue used for jointing a wire mesh and a metal mesh frame mainly comprises an acrylic acid and chloroprene rubber solvent glue system, a 502 system, a PE (polyethylene) and polyurethane hot melt adhesive and the like, wherein the chloroprene rubber solvent glue contains harmful volatile substances and is poor in stability, the acrylic acid glue is poor in high temperature resistance and water resistance, the quality guarantee period is short, and the polyurethane hot melt adhesive is large in construction energy consumption in the actual use process. The foreign Bi-component PU system glue of Beijing Ke and other brands has better effect, but has lower cost performance due to technical blockade and other reasons, and needs to develop a glue with equal application performance and better economic benefit.
Disclosure of Invention
Aiming at the problems of poor high temperature resistance, harmful volatile matter content, poor weather resistance and the like in the existing adhesive for bonding the silk screen and the metal screen frame, the invention provides the flexible single-component reaction type cold-sticking adhesive which has better performance, simple manufacture and good economic benefit. The cold-sticking adhesive adopts the mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate as the raw material, improves the overall performance of the cold-sticking adhesive, combines TPU and tackifying resin to complement other performances required by the cold-sticking adhesive, and ensures the strength after curing.
According to a first embodiment of the invention, a flexible single-component reactive cold-patch is provided.
A flexible single-component reaction type cold adhesive is prepared by mixing and reacting a polyurethane elastomer polymer (TPU), tackifying resin, isocyanate and an optional auxiliary agent in a solvent. The isocyanate is a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate.
Preferably, the mixing mass ratio of 2,3 '-diphenylmethane diisocyanate to 4,4' -diphenylmethane diisocyanate in the isocyanate is 60 to 98, preferably 70 to 95, 5 to 30, and more preferably 80 to 90.
Preferably, the cold adhesive tape comprises the following components:
8-20 parts of polyurethane elastomer polymer (TPU), preferably 9-18 parts, more preferably 10-15 parts;
2-20 parts of tackifying resin, preferably 3-15 parts, more preferably 4-12 parts;
2-15 parts of isocyanate, preferably 3-12 parts, and more preferably 4-10 parts;
0 to 3 parts of auxiliary agent, preferably 0.3 to 2 parts, and more preferably 0.5 to 1.5 parts;
60 to 95 parts of solvent, preferably 70 to 90 parts, and more preferably 75 to 80 parts.
Preferably, the polyurethane elastomeric polymer (TPU) is a fast crystallizing TPU and/or an ultra fast crystallizing TPU made up of alternating rigid blocks containing diisocyanate and flexible segments containing diisocyanate. Wherein the rigid diisocyanate-containing block is obtained by reacting a diisocyanate with a chain extender. The flexible segment containing diisocyanate is obtained by reacting diisocyanate with polyol.
Preferably, the diisocyanate is diphenylmethane diisocyanate (MDI) and/or Toluene Diisocyanate (TDI). The chain extender is one or more of glycerol, 1, 4-butanediol, 1, 6-hexanediol, triethylene glycol and hexamethylene diamine. The polyol is polyether polyol with the carbon content of 3-15.
Preferably, the auxiliary agent is one or more of an adhesion promoter, a coupling agent and a defoaming agent.
Preferably, the tackifying resin is one or more of C5-C9 petroleum resin and tert-butyl phenolic resin.
Preferably, the solvent is one or more of methyl acetate, ethyl acetate, acetone and diacetone alcohol.
Preferably, the accelerator is one or more of triethylene diamine, stannous octoate and dibutyltin dilaurate. The coupling agent is a silane coupling agent, preferably KH550 or A-1100 type silane coupling agent. The defoaming agent is a silicone defoaming agent, preferably a BYK141 type silicone defoaming agent.
According to a second embodiment provided by the invention, a preparation method of the flexible single-component reaction type cold-patch is provided.
A preparation method of a flexible single-component reaction type cold adhesive comprises the following steps:
1) Uniformly mixing a solvent, tackifying resin, polyurethane elastomer polymer (TPU), isocyanate and an optional auxiliary agent to obtain a mixture;
2) And adding isocyanate into the mixture for reaction to obtain the flexible single-component reaction type cold adhesive after the reaction is finished.
Preferably, in step 1), the solvent is one or more of methyl acetate, ethyl acetate, acetone, diacetone alcohol.
Preferably, the auxiliary agent is one or more of an adhesion promoter, a coupling agent and a defoaming agent. Preferably, the accelerator is one or more of triethylene diamine, stannous octoate and dibutyltin dilaurate. The coupling agent is a silane coupling agent. The defoaming agent is an organic silicon defoaming agent.
Preferably, the tackifying resin is one or more of C5-C9 petroleum resin and tert-butyl phenolic resin.
Preferably, the polyurethane elastomeric polymer (TPU) is a fast crystallizing TPU and/or an ultra fast crystallizing TPU having alternating rigid diisocyanate containing blocks and flexible diisocyanate containing segments. Wherein the rigid diisocyanate-containing block is obtained by reacting a diisocyanate with a chain extender. The soft segment containing diisocyanate is obtained by reacting diisocyanate and polyol. Preferably, the diisocyanate is diphenylmethane diisocyanate (MDI) and/or Toluene Diisocyanate (TDI). The chain extender is one or more of glycerol, 1, 4-butanediol, 1, 6-hexanediol and triethylene glycol. The polyol is polyether polyol with the carbon content of 3-15.
Preferably, in step 2), the isocyanate is a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate. Preferably, the mixing mass ratio of the 2,3 '-diphenylmethane diisocyanate to the 4,4' -diphenylmethane diisocyanate is 60 to 98, preferably 70 to 95.
Preferably, the addition amount of each component is as follows:
8 to 20 parts of polyurethane elastomer polymer (TPU), preferably 9 to 18 parts, and more preferably 10 to 15 parts;
2-20 parts of tackifying resin, preferably 3-15 parts, more preferably 4-12 parts;
2-15 parts of isocyanate, preferably 3-12 parts, and more preferably 4-10 parts;
0.1 to 3 parts of assistant, preferably 0.3 to 2 parts, and more preferably 0.5 to 1.5 parts;
the solvent is 60 to 95 parts, preferably 70 to 90 parts, and more preferably 75 to 80 parts.
Preferably, the ratio of isocyanate added in step 1) and step 2) is from 0.7 to 1.3, preferably from 0.8 to 1.2.
Preferably, the step 1) is specifically: adding a solvent, tackifying resin, polyurethane elastomer polymer (TPU), isocyanate and an auxiliary agent into a planetary kettle according to a certain proportion, and stirring and reacting for 1-3 h (preferably 1.5-2 h) under the conditions of 25-40 ℃ (preferably 25-30 ℃) and vacuum to obtain a mixture.
Preferably, the step 2) is specifically: and (3) filling nitrogen into the planetary kettle to break vacuum, adding isocyanate in proportion, sampling after reacting for 1-2 hours (preferably 1.3-1.8 hours) to detect the content of isocyanate groups, and stopping the reaction when the mass fraction of the isocyanate groups is less than 1% (preferably less than 0.5%), thus obtaining the flexible single-component reaction type cold adhesive.
According to a third embodiment provided by the invention, the application of the flexible single-component reaction type cold-patch adhesive is provided.
The application of the flexible single-component reaction type cold-patch adhesive is characterized in that the flexible single-component reaction type cold-patch adhesive is used for bonding silk fabrics or synthetic fibers with a metal frame. Preferably for bonding between nylon articles and aluminum alloy articles.
In the prior art, in the field of screen printing, most of glue adopted has performance defects, such as poor high temperature resistance and weather resistance or harmful substances, and the domestic existing glue is difficult to meet daily use requirements in the face of complex use environments, while the foreign two-component PU system glue of Beijing and other brands has extremely low cost performance.
In the invention, the mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate is adopted to prepare the flexible single-component reaction type cold adhesive, the mass ratio of the 2,3 '-diphenylmethane diisocyanate to the 4,4' -diphenylmethane diisocyanate is controlled to be 60-98.
According to the invention, the high temperature resistance, high humidity resistance and yellowing resistance after rapid crystallization are controlled by adjusting the synthesis route and raw materials of the TPU, and on the basis of a large number of experiments, the mixture of the ultrafast crystallization type polyether TPU and the fast crystallization type polyether TPU is selected, so that the prepared flexible single-component reaction type cold adhesive can be rapidly crystallized and has excellent weather resistance. Preferably, JM1012, JM2016, JM3011 and JM3015 of Ridak chemical research institute are selected as the ultrafast crystalline polyether TPU. JM3030, JT6011 and JT6029 are selected as the fast crystallization TPU.
In the invention, the volatilization speed of the cold adhesive tape is adjusted and the curing speed is corrected by changing the proportion of the solvent, and the required performance of the cold adhesive tape is supplemented by tackifying resin and functional auxiliary agent. Preferably, acetone, ethyl acetate and methyl acetate are selected as mixed solvents, and the tackifying resin is selected from SL-1410 of Huaqi chemical engineering, SC-2066 of Santa Lactoferrite and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. the flexible single-component reaction type cold adhesive provided by the invention is prepared from a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, has good high temperature resistance and humidity resistance, does not contain harmful volatile substances, is high in curing and drying speed and high in strength after curing, and can meet the daily use requirement.
2. The flexible single-component reaction type cold-patch adhesive provided by the invention is simple in preparation process, easy in raw material acquisition, low in cost and good in economic benefit.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
According to a first embodiment of the invention, a flexible single-component reactive cold-patch is provided.
A flexible single-component reactive cold adhesive is prepared by mixing and reacting a polyurethane elastomer polymer (TPU), tackifying resin, isocyanate and optionally an auxiliary agent in a solvent. The isocyanate is a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate.
Preferably, the mixing mass ratio of the 2,3 '-diphenylmethane diisocyanate to the 4,4' -diphenylmethane diisocyanate in the isocyanate is 60 to 98, preferably 70 to 95, and more preferably 80 to 90.
Preferably, the cold-pasting glue comprises the following components:
8 to 20 parts of polyurethane elastomer polymer (TPU), preferably 9 to 18 parts, and more preferably 10 to 15 parts;
2-20 parts of tackifying resin, preferably 3-15 parts, more preferably 4-12 parts;
2-15 parts of isocyanate, preferably 3-12 parts, and more preferably 4-10 parts;
0 to 3 parts of auxiliary agent, preferably 0.3 to 2 parts, and more preferably 0.5 to 1.5 parts;
the solvent is 60 to 95 parts, preferably 70 to 90 parts, and more preferably 75 to 80 parts.
Preferably, the polyurethane elastomeric polymer (TPU) is a fast crystallizing TPU and/or an ultra fast crystallizing TPU made up of alternating rigid blocks containing diisocyanate and flexible segments containing diisocyanate. Wherein the rigid block containing diisocyanate is obtained by reacting diisocyanate with a chain extender. The flexible segment containing diisocyanate is obtained by reacting diisocyanate with polyol.
Preferably, the diisocyanate is diphenylmethane diisocyanate (MDI) and/or Toluene Diisocyanate (TDI). The chain extender is one or more of glycerol, 1, 4-butanediol, 1, 6-hexanediol and triethylene glycol. The polyol is polyether polyol with the carbon content of 3-15.
Preferably, the auxiliary agent is one or more of an adhesion promoter, a coupling agent and a defoaming agent.
Preferably, the tackifying resin is one or more of C5-C9 petroleum resin and tert-butyl phenolic resin.
Preferably, the solvent is one or more of methyl acetate, ethyl acetate, acetone and diacetone alcohol.
Preferably, the accelerator is one or more of triethylene diamine, stannous octoate and dibutyltin dilaurate. The coupling agent is a silane coupling agent. The defoaming agent is an organic silicon defoaming agent.
According to a second embodiment provided by the invention, a preparation method of the flexible single-component reaction type cold adhesive is provided.
A preparation method of a flexible single-component reaction type cold-pasting adhesive comprises the following steps:
1) Uniformly mixing a solvent, tackifying resin, polyurethane elastomer polymer (TPU), isocyanate and an optional auxiliary agent to obtain a mixture;
2) And adding isocyanate into the mixture for reaction to obtain the flexible single-component reaction type cold-patch adhesive after the reaction is finished.
Preferably, in step 1), the solvent is one or more of methyl acetate, ethyl acetate, acetone, diacetone alcohol.
Preferably, the auxiliary agent is one or more of an adhesion promoter, a coupling agent and a defoaming agent. Preferably, the accelerator is one or more of triethylene diamine, stannous octoate and dibutyltin dilaurate. The coupling agent is a silane coupling agent. The defoaming agent is an organic silicon defoaming agent.
Preferably, the tackifying resin is one or more of C5-C9 petroleum resin and tert-butyl phenolic resin.
Preferably, the polyurethane elastomeric polymer (TPU) is a fast crystallizing TPU and/or an ultra fast crystallizing TPU made up of alternating rigid blocks containing diisocyanate and flexible segments containing diisocyanate. Wherein the rigid block containing diisocyanate is obtained by reacting diisocyanate with a chain extender. The flexible segment containing diisocyanate is obtained by reacting diisocyanate with polyol. Preferably, the diisocyanate is diphenylmethane diisocyanate (MDI) and/or Toluene Diisocyanate (TDI). The chain extender is one or more of glycerol, 1, 4-butanediol, 1, 6-hexanediol and triethylene glycol. The polyol is polyether polyol with the carbon content of 3-15.
Preferably, in step 2), the isocyanate is a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate. Preferably, the mixing mass ratio of the 2,3 '-diphenylmethane diisocyanate to the 4,4' -diphenylmethane diisocyanate is 60 to 98, preferably 70 to 95.
Preferably, the addition amount of each component is as follows:
8-20 parts of polyurethane elastomer polymer (TPU), preferably 9-18 parts, more preferably 10-15 parts;
2-20 parts of tackifying resin, preferably 3-15 parts, more preferably 4-12 parts;
2-15 parts of isocyanate, preferably 3-12 parts, and more preferably 4-10 parts;
0.1 to 3 parts of assistant, preferably 0.3 to 2 parts, and more preferably 0.5 to 1.5 parts;
the solvent is 60 to 95 parts, preferably 70 to 90 parts, and more preferably 75 to 80 parts.
Preferably, the ratio of isocyanate added in step 1) and step 2) is from 0.7 to 1.3, preferably from 0.8 to 1.2.
Preferably, the step 1) is specifically: adding a solvent, tackifying resin, polyurethane elastomer polymer (TPU), isocyanate and an auxiliary agent into a planetary kettle according to a certain proportion, and stirring and reacting for 1-3 h (preferably 1.5-2 h) under the conditions of 25-40 ℃ (preferably 25-30 ℃) and vacuum to obtain a mixture.
Preferably, the step 2) is specifically: and (3) filling nitrogen into the planetary kettle to break vacuum, adding isocyanate in proportion, sampling after reacting for 1-2 hours (preferably 1.3-1.8 hours) to detect the content of isocyanate groups, and stopping the reaction when the mass fraction of the isocyanate groups is less than 1% (preferably less than 0.5%), thus obtaining the flexible single-component reaction type cold adhesive.
According to a third embodiment provided by the invention, the application of the flexible single-component reaction type cold patch is provided.
The application of the flexible single-component reaction type cold-patch adhesive is characterized in that the flexible single-component reaction type cold-patch adhesive is used for bonding silk fabrics or synthetic fibers with a metal frame. Preferably for bonding between nylon articles and aluminum alloy articles.
Example 1
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Example 2
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoamer into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 6g of isocyanate consisted of 5.4g of 2,3 '-diphenylmethane diisocyanate and 0.6g of 4,4' -diphenylmethane diisocyanate.
Example 3
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 6g of the isocyanate consisted of 4.8g of 2,3 '-diphenylmethane diisocyanate and 1.2g of 4,4' -diphenylmethane diisocyanate.
Example 4
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoamer into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 6g of the isocyanate consisted of 4.2g of 2,3 '-diphenylmethane diisocyanate and 1.8g of 4,4' -diphenylmethane diisocyanate.
Example 5
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.7g of 2,3 '-diphenylmethane diisocyanate and 0.3g of 4,4' -diphenylmethane diisocyanate.
Example 6
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 4.8g of ultrafast crystal TPU4, 5.2g of fast crystal TPU5, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Example 7
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 4.5g of ultrafast crystal TPUs, 5.5g of fast crystal TPUs, 3g of isocyanate, 0.3g of adhesion promoters, 0.3g of coupling agents and 0.4g of antifoaming agents into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Example 8
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 2g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 2g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 4g of isocyanate consisted of 3.4g of 2,3 '-diphenylmethane diisocyanate and 0.6g of 4,4' -diphenylmethane diisocyanate.
Example 9
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 5g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 5g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 10g of isocyanate consisted of 8.5g of 2,3 '-diphenylmethane diisocyanate and 1.5g of 4,4' -diphenylmethane diisocyanate.
Example 10
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 1.5g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoamer into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 1.5g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 3g of isocyanate consisted of 2.6g of 2,3 '-diphenylmethane diisocyanate and 0.4g of 4,4' -diphenylmethane diisocyanate.
Example 11
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 6g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 6g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 12g of the isocyanate consisted of 10.2g of 2,3 '-diphenylmethane diisocyanate and 1.8g of 4,4' -diphenylmethane diisocyanate.
Example 12
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of phenolic resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Example 13
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 5g of C5 petroleum resin, 5g of phenolic resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 3g of isocyanate, 0.3g of adhesion promoter, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Example 14
1) Adding 20g of acetone, 40g of ethyl acetate, 40g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Example 15
1) Adding 35g of acetone, 35g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoamer into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Example 16
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 7.5g of ultrafast crystal TPU7, 7.5g of fast crystal TPU7, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Comparative example 1
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate were 2,3' -diphenylmethane diisocyanate.
Comparative example 2
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate were 4,4' -diphenylmethane diisocyanate.
Comparative example 3
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 6g of isocyanate consisted of 3g of 2,3 '-diphenylmethane diisocyanate and 3g of 4,4' -diphenylmethane diisocyanate.
Comparative example 4
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 6g of isocyanate consists of 2g2,3 '-diphenylmethane diisocyanate and 4g4,4' -diphenylmethane diisocyanate.
Comparative example 5
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 0.5g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 0.5g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Wherein 1g of the isocyanate consisted of 0.8g of 2,3 '-diphenylmethane diisocyanate and 0.2g of 4,4' -diphenylmethane diisocyanate.
Comparative example 6
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 10g of C5 petroleum resin, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Comparative example 7
1) Adding 20g of acetone, 30g of ethyl acetate, 30g of methyl acetate, 5g of ultrafast crystalline TPU, 5g of fast crystalline TPU, 0.3g of adhesion promoter, 3g of isocyanate, 0.3g of coupling agent and 0.4g of defoaming agent into a planetary kettle, controlling the temperature to be 30 ℃, stirring for 2 hours under a vacuum condition, and obtaining a mixture after stirring.
2) And (3) filling nitrogen into the planetary kettle to break vacuum, adding 3g of isocyanate, reacting for 1.5h, sampling, detecting that the content of isocyanate groups is lower than 0.5%, and stopping reaction to obtain the flexible single-component reaction type cold adhesive.
Of these, 6g of isocyanate consisted of 5.1g of 2,3 '-diphenylmethane diisocyanate and 0.9g of 4,4' -diphenylmethane diisocyanate.
Comparative example 8
Existing acrylic viscose.
Comparative example 9
The prior Beijing-Ke bi-component PU system adhesive.
The cold-bonded adhesives prepared in the examples 1 to 16 and the comparative examples 1 to 7 and the existing adhesives prepared in the comparative examples 8 and 9 are used for bonding the nylon mesh and the aluminum alloy frame, the curing speed and the bonding strength after curing are detected, the high-temperature resistance is detected, and the detection results are shown in the table below.
The flexible single-component reaction type cold adhesive provided by the invention has the advantages of good high temperature resistance and water resistance, high curing speed and high strength after curing, can meet the daily use requirement, and can obtain the optimal proportioning range of raw materials on the basis of a large number of experiments.
Claims (10)
1. The utility model provides a cold rubberizing of flexible single component reaction type which characterized in that: the cold-patch adhesive is obtained by mixing and reacting a polyurethane elastomer polymer (TPU), tackifying resin, isocyanate and optional auxiliary agent in a solvent; the isocyanate is a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate.
2. A cold-patch according to claim 1, wherein: the mixing mass ratio of the 2,3 '-diphenylmethane diisocyanate to the 4,4' -diphenylmethane diisocyanate in the isocyanate is 60-98, preferably 70-95 to 5-30, and more preferably 80-90.
3. A cold-applied glue according to claim 1 or 2, characterized in that: the cold-pasting glue comprises the following components:
8 to 20 parts of polyurethane elastomer polymer (TPU), preferably 9 to 18 parts, and more preferably 10 to 15 parts;
2-20 parts of tackifying resin, preferably 3-15 parts, and more preferably 4-12 parts;
2 to 15 parts of isocyanate, preferably 3 to 12 parts, and more preferably 4 to 10 parts;
0 to 3 parts of auxiliary agent, preferably 0.3 to 2 parts, and more preferably 0.5 to 1.5 parts;
the solvent is 60 to 95 parts, preferably 70 to 90 parts, and more preferably 75 to 80 parts.
4. A cold-patch according to any one of claims 1 to 3, wherein: the polyurethane elastomer polymer (TPU) is a fast crystallization type TPU and/or an ultra-fast crystallization type TPU which is formed by alternately forming a rigid block containing diisocyanate and a flexible chain segment containing diisocyanate; wherein the rigid block containing diisocyanate is obtained by reacting diisocyanate with a chain extender; the flexible chain segment containing diisocyanate is obtained by reacting diisocyanate and polyol;
preferably, the diisocyanate is diphenylmethane diisocyanate (MDI) and/or Toluene Diisocyanate (TDI);
the chain extender is one or more of glycerol, 1, 4-butanediol, 1, 6-hexanediol and triethylene glycol;
the polyol is polyether polyol with the carbon content of 3-15.
5. The cold patch according to claim 3 or 4, wherein: the auxiliary agent is one or more of adhesion promoter, coupling agent and defoaming agent; and/or
The tackifying resin is one or more of C5-C9 petroleum resin and tert-butyl phenolic resin; and/or
The solvent is one or more of methyl acetate, ethyl acetate, acetone and diacetone alcohol;
preferably, the accelerator is one or more of triethylene diamine, stannous octoate and dibutyltin dilaurate;
the coupling agent is a silane coupling agent;
the defoaming agent is an organic silicon defoaming agent.
6. A method of preparing a flexible one-component reactive cold plaster or a method of preparing a flexible one-component reactive cold plaster according to any of claims 1-5, characterized in that: the method comprises the following steps:
1) Uniformly mixing a solvent, tackifying resin, polyurethane elastomer polymer (TPU), isocyanate and optional auxiliary agent to obtain a mixture;
2) And adding isocyanate into the mixture for reaction to obtain the flexible single-component reaction type cold-patch adhesive after the reaction is finished.
7. The method of claim 6, wherein: in the step 1), the solvent is one or more of methyl acetate, ethyl acetate, acetone and diacetone alcohol; and/or
The auxiliary agent is one or more of adhesion promoter, coupling agent and defoaming agent; preferably, the accelerator is one or more of triethylene diamine, stannous octoate and dibutyltin dilaurate; the coupling agent is a silane coupling agent; the defoaming agent is an organic silicon defoaming agent; and/or
The tackifying resin is one or more of C5-C9 petroleum resin and tert-butyl phenolic resin; and/or
The polyurethane elastomer polymer (TPU) is a fast crystallization type TPU and/or an ultra-fast crystallization type TPU which is formed by alternately forming a rigid block containing diisocyanate and a flexible chain segment containing diisocyanate; wherein the rigid block containing diisocyanate is obtained by reacting diisocyanate and a chain extender; the flexible chain segment containing diisocyanate is obtained by reacting diisocyanate and polyol; preferably, the diisocyanate is diphenylmethane diisocyanate (MDI) and/or Toluene Diisocyanate (TDI); the chain extender is one or more of glycerol, 1, 4-butanediol, 1, 6-hexanediol and triethylene glycol; the polyol is polyether polyol with the carbon content of 3-15; and/or
In step 2), the isocyanate is a mixture of 2,3 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate; preferably, the mixing mass ratio of the 2,3 '-diphenylmethane diisocyanate to the 4,4' -diphenylmethane diisocyanate is 60 to 98, preferably 70 to 95.
8. The production method according to claim 6 or 7, characterized in that: the addition amount of each component is as follows:
8 to 20 parts of polyurethane elastomer polymer (TPU), preferably 9 to 18 parts, and more preferably 10 to 15 parts;
2-20 parts of tackifying resin, preferably 3-15 parts, and more preferably 4-12 parts;
2-15 parts of isocyanate, preferably 3-12 parts, and more preferably 4-10 parts;
0.1-3 parts of assistant, preferably 0.3-2 parts, and more preferably 0.5-1.5 parts;
60-95 parts of solvent, preferably 70-90 parts, and more preferably 75-80 parts;
preferably, the ratio of isocyanate added in step 1) and step 2) is from 0.7 to 1.3, preferably from 0.8 to 1.2.
9. The method for producing according to claim 8, characterized in that: the step 1) is specifically as follows: adding a solvent, tackifying resin, polyurethane elastomer polymer (TPU), isocyanate and an auxiliary agent into a planetary kettle in proportion, and stirring and reacting for 1-3 h (preferably 1.5-2 h) under the conditions of 25-40 ℃ (preferably 25-30 ℃) and vacuum to obtain a mixture; and/or
The step 2) is specifically as follows: and (3) filling nitrogen into the planetary kettle to break vacuum, adding isocyanate in proportion, sampling after reacting for 1-2 h (preferably 1.3-1.8 h) to detect the content of isocyanate groups, and stopping the reaction when the mass fraction of the isocyanate groups is lower than 1% (preferably lower than 0.5%), thus obtaining the flexible single-component reaction type cold adhesive.
10. Use of a flexible single-component reactive cold paste according to any of claims 1 to 5 or prepared according to the process of any of claims 6 to 9, characterized in that: the flexible single-component reactive cold-sticking adhesive is used for bonding silk fabrics or synthetic fibers with a metal framework; preferably for bonding between nylon articles and aluminum alloy articles.
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| CN113999641A (en) * | 2021-12-21 | 2022-02-01 | 浙江抟原复合材料有限公司 | Single-component moisture-curing polyurethane adhesive for ultralow-temperature environment and preparation method thereof |
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