CN115404036B - Moisture-curing polyurethane hot melt adhesive and preparation method thereof - Google Patents
Moisture-curing polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN115404036B CN115404036B CN202210034048.9A CN202210034048A CN115404036B CN 115404036 B CN115404036 B CN 115404036B CN 202210034048 A CN202210034048 A CN 202210034048A CN 115404036 B CN115404036 B CN 115404036B
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- 238000013008 moisture curing Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 187
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000012948 isocyanate Substances 0.000 claims abstract description 42
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 37
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 25
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 25
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 239000003963 antioxidant agent Substances 0.000 claims description 22
- 239000004611 light stabiliser Substances 0.000 claims description 22
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 15
- 208000005156 Dehydration Diseases 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000012943 hotmelt Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 22
- 125000004185 ester group Chemical group 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 10
- 125000000542 sulfonic acid group Chemical group 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical group C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006078 metal deactivator Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 quencher Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002023 wood Substances 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
- C09J175/06—Polyurethanes from polyesters
-
- 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
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Abstract
The invention relates to the field of hot melt adhesive preparation, and discloses a moisture-curing polyurethane hot melt adhesive and a preparation method thereof. The invention provides a moisture-curing polyurethane hot melt adhesive which comprises the following raw materials in parts by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate and 0.2-1 part of additive. The moisture-curing polyurethane hot melt adhesive prepared by the invention can directly bond the sample pieces in a low-temperature environment (25 ℃ and below), without heating the base material or regenerating the sample pieces, thereby being beneficial to reducing the production cost and improving the economic benefit.
Description
Technical Field
The invention relates to the field of hot melt adhesive preparation, in particular to a moisture-curing polyurethane hot melt adhesive and a preparation method thereof.
Background
The moisture-curing polyurethane hot melt adhesive is an adhesive formed by mixing polyurethane prepolymer blocked by isocyanate functional groups and various assistants, does not contain water and solvents, has the solid content of 100%, is a high-performance environment-friendly adhesive, and meets the increasingly strict environmental policy and requirements in China. The moisture-curing polyurethane hot melt adhesive is a cross-linking structural adhesive with high adhesive strength, can be positioned and cured quickly, has stronger initial adhesive force and has the special performances of water resistance, heat resistance, cold resistance, creep resistance, medium resistance and the like of a reactive adhesive.
The prior Chinese patent (CN 107488430A) discloses a moisture-curing polyurethane hot melt adhesive for coating the special-shaped surfaces of furniture and decorative components. The patent provides a moisture-curing polyurethane hot melt adhesive for coating special-shaped surfaces of furniture and decorative members, and the whole moisture-curing polyurethane hot melt adhesive has the advantages of high initial peel strength and final peel strength, good fluidity and strong positioning capability. However, the coating adhesive can provide stronger bonding capability in the early stage due to the addition of more strongly crystalline polyester polyol, but when a sample is coated in a low-temperature environment (25 ℃ and below), a heating device is additionally added to heat a coating substrate or recuperate the sample after coating is completed, so that good bonding of a PVC film or the substrate can be satisfied, and thus, the difficulty of machine adjustment of a coating process and the configuration cost of the heating device are increased.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides the moisture-curing polyurethane hot melt adhesive and the preparation method thereof, wherein the moisture-curing polyurethane hot melt adhesive prepared by the invention has high initial adhesion strength and final adhesion strength through unique raw material proportion and synthesis, has good fluidity and quick positioning effect, can be directly bonded without heating a base material or regenerating a sample in a low-temperature environment, and is beneficial to reducing production cost and improving economic benefit.
In order to achieve the above object, the present invention is achieved by the following technical means.
The invention provides a moisture-curing polyurethane hot melt adhesive, which comprises the following raw materials in parts by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate and 0.2-1 part of additive.
Preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, each of which has independently the structural formula:
wherein m in the first polyester polyol and the second polyester polyol are different positive integers, n is a positive integer which is independent respectively, a is a positive integer which is independent respectively, R 1 Each independently selected from any one of hydrogen group, carboxyl group, hydroxyl group, siloxyl group, ester group and sulfonic acid group, R 2 Each independently selected from any one of a siloxy group, a carboxyl group, an ester group, a hydroxyl group and a sulfonic acid group.
Preferably, the first polyester polyol has a structural formula wherein m is 3 to 5, n is 1 to 3, and a is 6 to 10;
preferably, the second polyester polyol has a structural formula wherein m is 2 to 4, n is 1 to 3, and a is 10 to 14;
preferably, the weight ratio of the first polyester polyol to the second polyester polyol is from 2 to 18:1.
preferably, the polyester polyol composition further comprises an auxiliary polyester polyol;
preferably, the auxiliary polyester polyol is an amorphous polyester polyol and/or a liquid polyester polyol;
preferably, the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the auxiliary polyester polyol is 2.25 to 11:1.
preferably, the tackifying resin is selected from at least one of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, modified rosin resin, and rosin;
preferably, the isocyanate is at least one selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethyl isophthalene diisocyanate and isophorone diisocyanate;
preferably, the additive is selected from at least one of a light stabilizer, an antioxidant and a metal deactivator.
The second aspect of the present invention provides a method for preparing a moisture-curable polyurethane hot melt adhesive, comprising the steps of:
(1) Mixing the polyester polyol composition, the tackifying resin and the additive, and then carrying out hot melting treatment and dehydration treatment to obtain a treatment liquid;
(2) Mixing the treatment liquid with isocyanate for reaction;
wherein the dosage of each raw material is as follows by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate and 0.2-1 part of additive.
Preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, each of which has independently the structural formula:
wherein the firstM in a polyester polyol and the second polyester polyol is a different positive integer, n is a positive integer which is independent of each other, a is a positive integer which is independent of each other, R 1 Each independently selected from any one of hydrogen group, carboxyl group, hydroxyl group, siloxyl group, ester group and sulfonic acid group, R 2 Each independently selected from any one of a siloxy group, a carboxyl group, an ester group, a hydroxyl group and a sulfonic acid group;
preferably, the first polyester polyol has a structural formula wherein m is 3 to 5, n is 1 to 3, and a is 6 to 10;
preferably, the second polyester polyol has a structural formula wherein m is 2 to 4, n is 1 to 3, and a is 10 to 14;
preferably, the weight ratio of the first polyester polyol to the second polyester polyol is from 2 to 18:1, a step of;
preferably, the polyester polyol composition further comprises an auxiliary polyester polyol;
preferably, the auxiliary polyester polyol is an amorphous polyester polyol and/or a liquid polyester polyol;
preferably, the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the auxiliary polyester polyol is 2.25 to 11:1.
preferably, the tackifying resin is selected from at least one of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, modified rosin resin, and rosin;
preferably, the isocyanate is at least one selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethyl isophthalene diisocyanate and isophorone diisocyanate;
preferably, the additive is selected from at least one of a light stabilizer, an antioxidant and a metal deactivator.
Preferably, in step (1), the hot-melt treatment is performed at a temperature of 140 to 150 ℃;
the conditions of the dehydration treatment at least comprise: vacuum degree is-0.095 MPa to-0.1 MPa, time is 1-2h, and stirring speed is 150-200rpm.
Preferably, in step (2), the conditions of the mixing reaction include at least: nitrogen protection, vacuum degree of-0.095 MPa to-0.1 MPa, temperature of 80-120 ℃, stirring speed of 150-200rpm;
preferably, in step (2), the condition for ending the mixing reaction process at least satisfies: the isocyanate content in the product reaches 1.8-2.2 wt%.
Through the technical scheme, the invention has the beneficial effects that: the moisture-curing polyurethane hot melt adhesive and the preparation method thereof provided by the invention have the advantages that the initial adhesion strength and the final adhesion strength of the moisture-curing polyurethane hot melt adhesive prepared by the invention are high through unique raw material proportion and synthesis, and the moisture-curing polyurethane hot melt adhesive has good fluidity and rapid positioning effect.
Furthermore, the moisture-curing polyurethane hot melt adhesive and the preparation method thereof provided by the invention have the advantages that the special groups are introduced into the main carbon chain through the molecular structure design of the first polyester polyol and the second polyester polyol, the molecular weight of the polyester polyol composition is controlled, and the problems that the substrate is required to be heated or the sample is required to be regenerated when the substrate is coated in a low-temperature environment are solved through the matched use of the first polyester polyol and the second polyester polyol, so that the energy and the cost are saved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a moisture-curing polyurethane hot melt adhesive, which comprises the following raw materials in parts by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate and 0.2-1 part of additive.
According to the present invention, preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, the first polyester polyol and the second polyester polyol each independently having the structural formula:
wherein m in the first polyester polyol and the second polyester polyol are different positive integers, n is a positive integer which is independent respectively, a is a positive integer which is independent respectively, R 1 Each independently selected from any one of hydrogen group, carboxyl group, hydroxyl group, siloxyl group, ester group and sulfonic acid group, R 2 Each independently selected from any one of a siloxy group, a carboxyl group, an ester group, a hydroxyl group and a sulfonic acid group. N in the first polyester polyol and the second polyester polyol may be the same or different, R 1 May be the same or different, R 2 May be the same or different, and a may be the same or different. Specifically, the ester group is a functional group of an ester in the carboxylic acid derivative, preferably a phthalic anhydride group.
According to the present invention, the first polyester polyol and the second polyester polyol are commercially available either directly or by the preparation methods disclosed in the prior art.
According to the present invention, preferably, the first polyester polyol has a structural formula in which m is 3 to 5, n is 1 to 3, and a is 6 to 10.
According to the present invention, preferably, the second polyester polyol has a structural formula in which m is 2 to 4, n is 1 to 3, and a is 10 to 14.
According to the present invention, preferably, the weight ratio of the first polyester polyol to the second polyester polyol is 2 to 18:1. the inventor finds that under the preferred embodiment, the initial adhesion strength and the final adhesion strength of the moisture-curing polyurethane hot melt adhesive are improved, the fluidity is good, and the positioning capability is strong.
According to the present invention, preferably, the polyester polyol composition further contains an auxiliary polyester polyol.
According to the present invention, preferably, the auxiliary polyester polyol is an amorphous polyester polyol and/or a liquid polyester polyol. Specifically, the auxiliary polyester polyol is an amorphous polyester polyol and a liquid polyester polyol. Amorphous polyester polyols and liquid polyester polyols are commercially available either directly or by the preparation methods disclosed in the prior art. For example, commercial products available for the amorphous polyester polyol are F-39030, F-37070, dynacoll-7130, dynacoll-7140, etc.; commercial products which can be used for the liquid polyester polyol are F-37030, XCP-2000IPS, dynacoll-7250, dynacoll-7230 and the like.
According to the present invention, preferably, the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the auxiliary polyester polyol is 2.25 to 11:1.
according to the invention, the tackifying resin can accelerate the hot melt gelation polymerization when the moisture-curable polyurethane hot melt adhesive is cooled, thereby being beneficial to improving the initial adhesive strength of the moisture-curable polyurethane hot melt adhesive. Preferably, the tackifying resin is selected from at least one of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, modified rosin resin, and rosin. More preferably, the tackifying resin is selected from the group consisting of modified rosin resins that are commercially available, for example, as commercially available products SNS-138, SNS-145, YH-100C, and the like.
According to the present invention, preferably, the isocyanate is at least one selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylm-xylylene diisocyanate and isophorone diisocyanate, and such isocyanates may be used alone or in combination, more preferably, the isocyanate is diphenylmethane diisocyanate.
According to the invention, the addition of the additive can improve the heat resistance of the moisture-curing polyurethane hot melt adhesive, adjust the bonding strength, reduce shrinkage, prevent self adhesion and reduce the cost. Preferably, the additive is selected from at least one of a light stabilizer, an antioxidant and a metal deactivator, more preferably a light stabilizer and an antioxidant. Light stabilizers and antioxidants are commercially available, for example, commercial products useful for the antioxidants are 1076, 1010, 264, 2246, etc.; the light stabilizer is one or more of light shielding agent, ultraviolet absorbent, quencher, free radical scavenger and hydroperoxide decomposer, and commercially available products include AM-101, GW-540, JF-90, HPT, etc.
The second aspect of the invention provides a method for preparing a moisture-curable polyurethane hot melt adhesive, which comprises the following steps:
(1) Mixing the polyester polyol composition, the tackifying resin and the additive, and then carrying out hot melting treatment and dehydration treatment to obtain a treatment liquid;
(2) Mixing the treatment liquid with isocyanate for reaction;
wherein the dosage of each raw material is as follows by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate and 0.2-1 part of additive.
According to the present invention, preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, the first polyester polyol and the second polyester polyol each independently having the structural formula:
wherein m in the first polyester polyol and the second polyester polyol are different positive integers, n is a positive integer which is independent respectively, a is a positive integer which is independent respectively, R 1 Each independently selected from any one of hydrogen group, carboxyl group, hydroxyl group, siloxyl group, ester group and sulfonic acid group, R 2 Each independently selected from any one of a siloxy group, a carboxyl group, an ester group, a hydroxyl group and a sulfonic acid group.
According to the present invention, preferably, the first polyester polyol has a structural formula in which m is 3 to 5, n is 1 to 3, and a is 6 to 10.
According to the present invention, preferably, the second polyester polyol has a structural formula in which m is 2 to 4, n is 1 to 3, and a is 10 to 14.
According to the present invention, preferably, the weight ratio of the first polyester polyol to the second polyester polyol is 2 to 18:1.
according to the present invention, preferably, the polyester polyol composition further contains an auxiliary polyester polyol.
According to the present invention, preferably, the auxiliary polyester polyol is an amorphous polyester polyol and/or a liquid polyester polyol.
According to the present invention, preferably, the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the auxiliary polyester polyol is 2.25 to 11:1.
according to the present invention, preferably, the tackifying resin is selected from at least one of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, modified rosin resin, and rosin.
According to the present invention, preferably, the isocyanate is at least one selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylm-xylylene diisocyanate and isophorone diisocyanate.
According to the present invention, preferably, the additive is selected from at least one of a light stabilizer, an antioxidant, and a metal deactivator.
According to the invention, the above substances are all commercially available.
According to the present invention, preferably, in the step (1), the temperature of the hot-melt treatment is 140 to 150 ℃, and specifically may be 140 ℃, 142 ℃, 144 ℃, 146 ℃, 148 ℃, 150 ℃ or any value between the foregoing values; the conditions of the dehydration treatment at least comprise: the vacuum degree is-0.095 MPa to-0.1 MPa, and can be specifically-0.095 MPa, -0.096MPa, -0.097MPa, -0.098MPa, -0.099MPa, -0.1MPa or any value between the foregoing values; the time is 1-2h, and can be specifically 1h, 1.5h, 2h or any value between the above values; the stirring speed is 150-200rpm, and may be specifically 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm or any value between the foregoing values.
According to the present invention, preferably, in step (2), the conditions of the mixing reaction include: nitrogen protection, wherein the vacuum degree is-0.095 MPa to-0.1 MPa, and can be specifically-0.095 MPa, -0.096MPa, -0.097MPa, -0.098MPa, -0.099MPa, -0.1MPa or any value between the foregoing values; the temperature is 80-120deg.C, and can be 80deg.C, 90deg.C, 100deg.C, 110deg.C, 120deg.C or any value between the above values; the stirring speed is 150-200rpm, and may be specifically 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm or any value between the foregoing values.
According to the present invention, preferably, in step (2), the condition for ending the mixing reaction process at least satisfies: the isocyanate content in the product reaches 1.8-2.2 wt%.
According to the invention, the determination of the isocyanate content in the product is carried out according to HG/T2409-92.
According to a particularly preferred embodiment of the present invention, the method for preparing a moisture-curable polyurethane hot melt adhesive comprises the steps of:
(1) Mixing the polyester polyol composition, the tackifying resin and the additive, performing hot melting treatment at 140-150 ℃, and performing dehydration treatment at a vacuum degree of-0.095 MPa to-0.1 MPa and a stirring rotation speed of 150-200rpm for 1-2 hours to obtain a treatment liquid;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, and carrying out mixed reaction under the conditions of vacuum degree of-0.095 MPa to-0.1 MPa, temperature of 80-120 ℃ and stirring rotation speed of 150-200rpm until the mass percent of isocyanate in the product reaches 1.8-2.2%, and stopping the reaction;
the raw materials are used in parts by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate and 0.2-1 part of additive;
the polyester polyol composition contains a first polyester polyol, a second polyester polyol, an amorphous polyester polyol, and a liquid polyester polyol;
the structural formulas of the first polyester polyol and the second polyester polyol are respectively and independently:
wherein m in the first polyester polyol and the second polyester polyol are different positive integers, n is a positive integer which is independent, a is a different positive integer, R 1 Each independently selected from any one of hydrogen group, carboxyl group, hydroxyl group, siloxyl group, ester group and sulfonic acid group, R 2 Each independently selected from any one of a siloxy group, a carboxyl group, an ester group, a hydroxyl group and a sulfonic acid group;
the first polyester polyol has a structural formula of m is 3-5, n is 1-3, and a is 6-10; the structural formula of the second polyester polyol is that m is 2-4, n is 1-3, and a is 10-14;
the weight ratio of the first polyester polyol to the second polyester polyol is 2 to 18:1, a step of; the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the total amount of the amorphous polyester polyol and the liquid polyester polyol is 2.25-11:1.
in the particularly preferred embodiment, the preparation method of the moisture-curing polyurethane hot melt adhesive has the advantages of simple process and low cost, and the product is convenient to store and transport through the later dehydration treatment step, so that the stability of the product performance is effectively maintained.
The present invention will be described in detail by examples.
The reagents involved in the examples and comparative examples of the present invention are described below:
in the following examples, the first polyester polyol was purchased from XU.S. chemical (Suzhou) and was available under the designations XCP-2000IPS, XCP-2000PM, XCP-PA110N; the second polyester polyol is available from XCPO-3000N, XCP-3000H, XCPA-195; amorphous polyester polyol is available from Yingchuang specialty Chemie (Shanghai) Co., ltd, model Dynacoll-7130; liquid polyester polyol is purchased from Shanghai specialty Chemie, inc., model Dynacoll-7250; crystalline polyester polyols are available from XU CHANNEL, inc. under the model numbers XCP-44, XCP-3000B; the modified rosin resin is purchased from Shenzhen chemical industry Co., ltd, and the model is YH-100C; isocyanate is purchased from basf polyurethane (Chongqing) limited company and is model number MS-C; light stabilizers were purchased from Tokubei chemical industries, inc., model JF-90; the antioxidant is purchased from Tianjin An Long New Material Co., ltd, and is of the type RIANOX 1010; some commercially available moisture-curable polyurethane hot melt adhesives are available from XCUR chemical (Suzhou) under the model XCUR-6018.
In the following examples, 1 part by weight represents 1g.
Example 1
(1) Mixing the first polyester polyol, the second polyester polyol, the amorphous polyester polyol, the liquid polyester polyol, the modified rosin resin, the light stabilizer and the antioxidant, performing hot melting treatment at 145 ℃, and performing dehydration treatment at-0.098 MPa of vacuum degree and 175rpm of stirring speed for 1.5 hours to obtain a treatment liquid;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, and carrying out a mixing reaction under the conditions of vacuum degree of-0.098 MPa, temperature of 100 ℃ and stirring rotation speed of 175rpm until the mass percent of the isocyanate in the product reaches 2.0%, and stopping the reaction;
the raw materials are used in parts by weight: 70 parts of a first polyester polyol (XCP-2000 IPS), 10 parts of a second polyester polyol (XCP-3000N), 10 parts of an amorphous polyester polyol (Dynacoll-7130), 10 parts of a liquid polyester polyol (Dynacoll-7250), 6 parts of a modified rosin resin (YH-100C), 13.5 parts of isocyanate (MS-C), 0.25 parts of a light stabilizer (JF-90) and 0.25 parts of an antioxidant (RIANOX 1010);
wherein R in the structural formula of the first polyester polyol 1 Is phthalic anhydride group, R 2 Hydroxy, m=4, n=2, a=8, xcp-2000IPS (hydroxyl value 53-59 mgKOH/g), molecular weight about 2000; r in the structural formula of the second polyester polyol 1 Is phthalic anhydride group, R 2 Is hydroxy, m=3, n=2, a=12, model XCP-3000N (hydroxyl value 35-39 mgKOH/g), molecular weight about 3000.
Example 2
(1) Mixing a first polyester polyol, a second polyester polyol, an amorphous polyester polyol, a liquid polyester polyol, a modified rosin resin, a light stabilizer and an antioxidant, performing hot melting treatment at 150 ℃, and performing dehydration treatment at a vacuum degree of-0.1 MPa and a stirring frequency of 200rpm for 1h to obtain a treatment liquid;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, and carrying out a mixing reaction under the conditions of vacuum degree of-0.1 MPa, temperature of 80 ℃ and stirring frequency of 200rpm until the mass percent of the isocyanate in the product reaches 1.8%, and stopping the reaction;
the raw materials are used in parts by weight: 30 parts of a first polyester polyol (XCP-2000 IPS), 15 parts of a second polyester polyol (XCP-3000N), 10 parts of an amorphous polyester polyol (Dynacoll-7130), 10 parts of a liquid polyester polyol (Dynacoll-7250), 5 parts of a modified rosin resin (YH-100C), 10 parts of isocyanate (MS-C), 0.1 part of a light stabilizer (JF-90) and 0.1 part of an antioxidant (RIANOX 1010).
Example 3
(1) Mixing a first polyester polyol, a second polyester polyol, an amorphous polyester polyol, a liquid polyester polyol, a modified rosin resin, a light stabilizer and an antioxidant, performing hot melting treatment at 140 ℃, and performing dehydration treatment at a vacuum degree of-0.095 MPa and a stirring rotation speed of 150rpm for 2 hours to obtain a treatment liquid;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, and carrying out a mixing reaction under the conditions of vacuum degree of-0.095 MPa, temperature of 120 ℃ and stirring rotation speed of 150rpm until the mass percent of the isocyanate in the product reaches 2.2%, and stopping the reaction;
the raw materials are used in parts by weight: first polyester polyol type (XCP-2000 PM)
90 parts of a second polyester polyol (model XCP-3000H), 5 parts of an amorphous polyester polyol (Dynacoll-7130), 4.3 parts of a liquid polyester polyol (Dynacoll-7250), 10 parts of a modified rosin resin (YH-100C), 25 parts of isocyanate (MS-C), 0.5 part of a light stabilizer (JF-90) and 0.5 part of an antioxidant (RIANOX 1010);
wherein R in the structural formula of the first polyester polyol 1 Is phthalic anhydride group, R 2 Is hydroxy, m=5, n=3, a=7, model XCP-2000PM (hydroxyl value 53-59 mgKOH/g), molecular weight about2000; r in the structural formula of the second polyester polyol 1 Is phthalic anhydride group, R 2 Is hydroxy, m=2, n=2, a=14, model XCP-3000H (hydroxyl value 34-40 mgKOH/g), molecular weight about 3000.
Example 4
A moisture-curable polyurethane hot melt adhesive was prepared as in example 1, except that the amounts of the raw materials were as follows in parts by weight: 70 parts of a first polyester polyol (model XCP-PA 110N), 10 parts of a second polyester polyol (model XCPA-195), 10 parts of an amorphous polyester polyol (Dynacoll-7130), 10 parts of a liquid polyester polyol (Dynacoll-7250), 6 parts of a modified rosin resin (YH-100C), 13.5 parts of isocyanate (MS-C), 0.25 part of a light stabilizer (JF-90) and 0.25 part of an antioxidant (RIANOX 1010);
wherein R in the structural formula of the first polyester polyol 1 Is phthalic anhydride group, R 2 Is hydroxyl, m=8, n=4, a=3, model XCP-PA110N (hydroxyl number 104-110 mgKOH/g), molecular weight about 1000; r in the structural formula of the second polyester polyol 1 Is phthalic anhydride group, R 2 Is hydroxy, m=5, n=4, a=2, model XCPA-195 (hydroxyl value 190-205 mgKOH/g), molecular weight about 560.
Example 5
A moisture-curable polyurethane hot melt adhesive was prepared as in example 1, except that the amounts of the raw materials were as follows in parts by weight: 40 parts of a first polyester polyol (XCP-2000 IPS), 40 parts of a second polyester polyol (XCP-3000N), 20 parts of an amorphous polyester polyol (Dynacoll-7130), 20 parts of a liquid polyester polyol (Dynacoll-7250), 6 parts of a modified rosin resin (YH-100C), 13.5 parts of isocyanate (MS-C), 0.25 parts of a light stabilizer (JF-90) and 0.25 part of an antioxidant (RIANOX 1010).
Example 6
A moisture-curable polyurethane hot melt adhesive was prepared as in example 1, except that the amounts of the raw materials were as follows in parts by weight: 70 parts of first polyester polyol (XCP-2000 IPS), 10 parts of second polyester polyol (XCP-3000N), 6 parts of modified rosin resin (YH-100C), 13.5 parts of isocyanate (MS-C), 0.25 part of light stabilizer (JF-90) and 0.25 part of antioxidant (RIANOX 1010).
Comparative example 1
(1) Mixing crystalline polyester polyol, modified rosin resin, light stabilizer and antioxidant, performing hot melting treatment at 145 ℃, and performing dehydration treatment at-0.098 MPa and 175rpm for 1.5h to obtain a treatment liquid;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, and carrying out a mixing reaction under the conditions of vacuum degree of-0.098 MPa, temperature of 100 ℃ and stirring rotation speed of 175rpm until the mass percent of the isocyanate in the product reaches 2.0%, and stopping the reaction;
the raw materials are used in parts by weight: 20 parts of crystalline polyester polyol (XCP-44), 20 parts of crystalline polyester polyol (XCP-3000B), 6 parts of modified rosin resin (YH-100C), 13.5 parts of isocyanate (MS-C), 0.25 part of light stabilizer (JF-90) and 0.25 part of antioxidant (RIANOX 1010).
Comparative example 2
Mixing the first polyester polyol, the second polyester polyol, the amorphous polyester polyol, the liquid polyester polyol, isocyanate, modified rosin resin, a light stabilizer and an antioxidant, performing hot melting treatment at 145 ℃, and performing dehydration treatment at a vacuum degree of-0.098 MPa and a stirring frequency of 75Hz until the mass percentage of isocyanate in the product reaches 2.0%, and stopping the reaction;
the raw materials are used in parts by weight: 70 parts of first polyester polyol (XCP-2000 IPS), 10 parts of second polyester polyol (XCP-3000N), 10 parts of amorphous polyester polyol (Dynacoll-7130), 10 parts of liquid polyester polyol (Dynacoll-7250), 6 parts of modified rosin resin (YH-100C), 13.5 parts of isocyanate (MS-C), 0.25 part of light stabilizer (JF-90) and 0.25 part of antioxidant (RIANOX 1010).
Comparative example 3
Some commercially available moisture curable polyurethane hot melt adhesive (XCUR-6018).
Test case
The moisture-curable polyurethane hot melt adhesives prepared in example 1 to example 6 and comparative example 1 to comparative example 3 were tested for viscosity, open time, initial peel strength and final peel strength, and the results are shown in table 1.
The moisture-curable polyurethane hot melt adhesives prepared in example 1 to example 6 and comparative example 1 to comparative example 3 were subjected to PVC film/wood plastic panel adhesion performance test, and the results are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from the results of tables 1 and 2, the moisture-curable polyurethane hot melt adhesives obtained by the preparation methods provided in examples 1 to 6 showed better initial peel strength and higher final peel strength than those of comparative examples 1 to 3, and the adhesive effect was significantly improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (5)
1. The moisture-curing polyurethane hot melt adhesive is characterized by comprising the following raw materials in parts by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate and 0.2-1 part of additive;
wherein the polyester polyol composition is composed of a first polyester polyol, a second polyester polyol and an auxiliary polyester polyol, wherein the first polyester polyol is purchased from XCPS-2000 IPS, XCPS-2000 PM or XCPPA 110N; the second polyester polyol is available from XCPO-3000N, XCP-3000H or XCPA-195; the weight ratio of the first polyester polyol to the second polyester polyol is 2-18:1, a step of; the additive is at least one selected from light stabilizer, antioxidant and metal passivator;
the preparation method of the moisture-curing polyurethane hot melt adhesive comprises the following steps:
(1) Mixing the polyester polyol composition, the tackifying resin and the additive, and then carrying out hot melting treatment and dehydration treatment to obtain a treatment liquid;
(2) And mixing the treatment liquid with isocyanate for reaction.
2. The moisture-curable polyurethane hot melt adhesive of claim 1, wherein the auxiliary polyester polyol is an amorphous polyester polyol and/or a liquid polyester polyol;
the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the auxiliary polyester polyol is 2.25 to 11:1.
3. the moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein the tackifying resin is selected from at least one of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, modified rosin resin, and rosin;
the isocyanate is at least one selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethyl isophthalene diisocyanate and isophorone diisocyanate.
4. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein in step (1), the hot melt treatment is performed at a temperature of 140 to 150 ℃;
the conditions of the dehydration treatment at least comprise: vacuum degree is-0.095 MPa to-0.1 MPa, time is 1-2h, and stirring speed is 150-200rpm.
5. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein in step (2), the conditions of the mixing reaction include at least: nitrogen protection, vacuum degree of-0.095 MPa to-0.1 MPa, temperature of 80-120 ℃, stirring speed of 150-200rpm;
in step (2), the condition for ending the mixing reaction process at least satisfies: the isocyanate content in the product reaches 1.8-2.2 wt%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107488430A (en) * | 2017-09-08 | 2017-12-19 | 广州市极威新材料有限公司 | A kind of moisture-curable polyurethane hot melt adhesive coated for furniture and decoration element shaped face |
| CN107523255A (en) * | 2017-09-08 | 2017-12-29 | 广州市极威新材料有限公司 | A kind of moisture-curable polyurethane hot melt adhesive for faced deorative |
| CN110607160A (en) * | 2019-08-20 | 2019-12-24 | 上海汉司实业有限公司 | Moisture-curing polyurethane hot melt adhesive for automobile ceiling pendant and preparation method thereof |
| CN112646530A (en) * | 2020-12-18 | 2021-04-13 | 黄世斌 | Moisture-curing hot melt adhesive capable of being rapidly cured at low temperature |
| CN112694861A (en) * | 2020-12-25 | 2021-04-23 | 重庆中科力泰高分子材料股份有限公司 | Preparation method of viscosity-controllable moisture-curable polyurethane hot melt adhesive and product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107488430A (en) * | 2017-09-08 | 2017-12-19 | 广州市极威新材料有限公司 | A kind of moisture-curable polyurethane hot melt adhesive coated for furniture and decoration element shaped face |
| CN107523255A (en) * | 2017-09-08 | 2017-12-29 | 广州市极威新材料有限公司 | A kind of moisture-curable polyurethane hot melt adhesive for faced deorative |
| CN110607160A (en) * | 2019-08-20 | 2019-12-24 | 上海汉司实业有限公司 | Moisture-curing polyurethane hot melt adhesive for automobile ceiling pendant and preparation method thereof |
| CN112646530A (en) * | 2020-12-18 | 2021-04-13 | 黄世斌 | Moisture-curing hot melt adhesive capable of being rapidly cured at low temperature |
| CN112694861A (en) * | 2020-12-25 | 2021-04-23 | 重庆中科力泰高分子材料股份有限公司 | Preparation method of viscosity-controllable moisture-curable polyurethane hot melt adhesive and product thereof |
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