CN115404036A - 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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- CN115404036A CN115404036A CN202210034048.9A CN202210034048A CN115404036A CN 115404036 A CN115404036 A CN 115404036A CN 202210034048 A CN202210034048 A CN 202210034048A CN 115404036 A CN115404036 A CN 115404036A
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- polyester polyol
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- hot melt
- melt adhesive
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 44
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 238000013008 moisture curing Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 216
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 59
- 239000012948 isocyanate Substances 0.000 claims abstract description 44
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 30
- 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 23
- 239000004611 light stabiliser Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 14
- 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 10
- 230000008018 melting Effects 0.000 claims description 10
- 125000004185 ester group Chemical group 0.000 claims description 8
- 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 7
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 7
- 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 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000006078 metal deactivator Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 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 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 239000012943 hotmelt Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 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 6
- 150000003254 radicals Chemical class 0.000 description 6
- -1 ester radical Chemical class 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 206010066054 Dysmorphism Diseases 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber 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 preparation of hot melt adhesives, and discloses a moisture-curable polyurethane hot melt adhesive and a preparation method thereof. The invention provides a moisture-curable 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. When the moisture-curing polyurethane hot melt adhesive prepared by the invention is used for coating a sample piece in a low-temperature environment (below 25 ℃), the substrate is not required to be heated or the sample piece is not required to be reheated and is directly bonded, so that the production cost is reduced, and the economic benefit is improved.
Description
Technical Field
The invention relates to the field of preparation of hot melt adhesives, and particularly relates to a moisture-curable polyurethane hot melt adhesive and a preparation method thereof.
Background
The moisture-curing polyurethane hot melt adhesive is an adhesive formed by mixing a polyurethane prepolymer containing an isocyanate functional group end capping and a plurality of auxiliary agents, does not contain water and solvent, has a solid content of 100 percent, is a high-performance environment-friendly adhesive, and meets increasingly strict environmental policies and requirements in China. The moisture-curing polyurethane hot melt adhesive is a cross-linking type structural adhesive with high bonding strength, can be quickly positioned and quickly cured, has relatively strong initial adhesion, and has the water resistance, heat resistance, cold resistance, creep resistance, medium resistance and other properties of a reaction type adhesive.
The prior Chinese patent (CN 107488430A) discloses a moisture-curing polyurethane hot melt adhesive for covering special-shaped surfaces of furniture and decorative components. This patent provides a moisture-cure polyurethane hot melt adhesive that is used for furniture and decoration component dysmorphism face cladding, and whole moisture-cure polyurethane hot melt adhesive demonstrates the advantage that initial peel strength and final peel strength are high, and mobility is good, and the positional capability is strong. However, since more strong crystalline polyester polyol is added to the coating adhesive, although a strong adhesive capacity can be provided in the previous period, when a sample is coated in a low-temperature environment (25 ℃ or below), an additional heating device is required to heat the coating substrate or the sample is reheated after coating is completed, so that good adhesion to a PVC film or a substrate can be satisfied, and thus, the machine adjustment difficulty of the 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.
In order to achieve the above object, the present invention is obtained 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 comprises a first polyester polyol and a second polyester polyol, each of the first polyester polyol and the second polyester polyol independently having the structural formula:
wherein m in the first polyester polyol and the second polyester polyol is different positive integers, n is respectively independent positive integer, a is respectively independent positive integer, R 1 Each independently selected from any one of hydrogen radical, carboxyl, hydroxyl, siloxy, ester radical and sulfonic radical, 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 structure in which m is 3 to 5, n is 1 to 3, a is 6 to 10;
preferably, the second polyester polyol has a structure wherein m is 2 to 4, n is 1 to 3, 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 from 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 selected from at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethyl m-xylylene 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 invention provides a preparation method of a moisture-curing polyurethane hot melt adhesive, which comprises the following steps:
(1) Mixing a polyester polyol composition, tackifying resin and an additive, and then carrying out hot melting treatment and dehydration treatment to obtain a treatment fluid;
(2) Mixing the treatment liquid with isocyanate for reaction;
wherein the dosage of each raw material is as follows according to the weight portion: 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 comprises a first polyester polyol and a second polyester polyol, each of the first polyester polyol and the second polyester polyol independently having the structural formula:
wherein m in the first polyester polyol and the second polyester polyol is different positive integers, n is respectively independent positive integer, a is respectively independent positive integer, R 1 Each independently selected from any one of hydrogen radical, carboxyl, hydroxyl, siloxy, ester radical and sulfonic radical, R 2 Each independently selected from any one of a siloxy group, a carboxyl group, an ester group, a hydroxyl group and a sulfonic group;
preferably, the first polyester polyol has a structure in which m is 3 to 5, n is 1 to 3, a is 6 to 10;
preferably, the second polyester polyol has a structure wherein m is 2 to 4, n is 1 to 3, 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 from 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 selected from at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylm-xylylene 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 the step (1), the hot-melt treatment is performed at a temperature of 140 to 150 ℃;
the conditions of the dehydration treatment at least include: the vacuum degree is between-0.095 MPa and-0.1 MPa, the time is 1 to 2 hours, and the stirring speed is 150 to 200rpm.
Preferably, in step (2), the conditions of the mixing reaction at least include: under the protection of nitrogen, the vacuum degree is-0.095 MPa to-0.1 MPa, the temperature is 80 ℃ to 120 ℃, and the stirring speed is 150rpm to 200rpm;
preferably, in the step (2), the condition for ending the mixing reaction process at least satisfies: the isocyanate content in the product amounts to 1.8-2.2% by weight.
Through the technical scheme, the invention has the beneficial effects that: according to the moisture-curing polyurethane hot melt adhesive and the preparation method thereof provided by the invention, through unique raw material proportion and synthesis, the initial adhesive strength and the final adhesive strength of the moisture-curing polyurethane hot melt adhesive prepared by the invention are high, and the moisture-curing polyurethane hot melt adhesive has good fluidity and a rapid positioning effect.
Furthermore, according to the moisture-curing polyurethane hot melt adhesive and the preparation method thereof provided by the invention, through the molecular structure design of the first polyester polyol and the second polyester polyol, a special group is introduced into the main carbon chain, the molecular weight of the polyester polyol composition is controlled, and through the matched use of the first polyester polyol and the second polyester polyol, the problem that a base material needs to be heated or a sample needs to be reheated during coating in a low-temperature environment is solved, and energy and cost are saved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should 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, each of the structural formulae of the first polyester polyol and the second polyester polyol being independently:
wherein m in the first polyester polyol and the second polyester polyol is different positive integers, n is respectively independent positive integer, a is respectively independent positive integer, R 1 Each independently selected from any one of hydrogen radical, carboxyl, hydroxyl, siloxy, ester radical and sulfonic radical, 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, and 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 a carboxylic acid derivative, and is preferably a benzene anhydride group.
According to the present invention, the first polyester polyol and the second polyester polyol are either directly commercially available or can be prepared by a preparation method disclosed in the prior art.
According to the present invention, preferably, the first polyester polyol has a structure 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 structure in which m is 2 to 4, n is 1 to 3, and a is 10 to 14.
According to the invention, preferably, the weight ratio of the first polyester polyol to the second polyester polyol is from 2 to 18:1. the inventor finds that the initial adhesive strength and the final adhesive strength of the moisture-curing polyurethane hot melt adhesive are improved, and the moisture-curing polyurethane hot melt adhesive is good in fluidity and strong in positioning capability.
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 amorphous polyester polyol and liquid polyester polyol. Amorphous polyester polyols and liquid polyester polyols are either directly commercially available or can be prepared by methods known in the art. For example, F-39030, F-37070, dynacoll-7130, dynacoll-7140, and the like are commercially available products for the amorphous polyester polyol; the liquid polyester polyol can be used as commercial products such as 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 is added to accelerate the condensation of the moisture-curing polyurethane hot melt adhesive when the moisture-curing polyurethane hot melt adhesive is cooled, so that the initial adhesion strength of the moisture-curing polyurethane hot melt adhesive is improved. Preferably, the tackifying resin is selected from at least one of C5 petroleum resins, C9 petroleum resins, hydrogenated petroleum resins, modified rosin resins and rosins. More preferably, the tackifying resin is selected from modified rosin resins, which are commercially available, for example, SNS-138, SNS-145, YH-100C, etc. are commercially available.
According to the present invention, preferably, the isocyanate is selected from at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylm-xylylene diisocyanate and isophorone diisocyanate, and such isocyanates may be used alone or in combination, and more preferably, the isocyanate is diphenylmethane diisocyanate.
According to the invention, the additive is added, so that the heat resistance of the moisture-curing polyurethane hot melt adhesive can be improved, the bonding strength can be adjusted, the shrinkage can be reduced, the self-adhesion can be prevented, and the cost can be reduced. 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. Both the light stabilizer and the antioxidant are commercially available, and for example, 1076, 1010, 264, 2246, etc. are commercially available as the antioxidant; the light stabilizer is one or more of a light shielding agent, an ultraviolet absorber, a quenching agent, a free radical trapping agent and a hydroperoxide decomposer, and the available commercial products are AM-101, GW-540, JF-90, HPT and the like.
The second aspect of the invention provides a preparation method of a moisture-curing polyurethane hot melt adhesive, which comprises the following steps:
(1) Mixing the polyester polyol composition, tackifying resin and additive, and then carrying out hot melting treatment and dehydration treatment to obtain a treatment solution;
(2) Mixing the treatment liquid with isocyanate for reaction;
wherein the dosage of each raw material is as follows according to the weight portion: 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, each of the structural formulae of the first polyester polyol and the second polyester polyol being independently:
wherein m in the first polyester polyol and the second polyester polyol is different positive integers, n is respectively independent positive integer, a is respectively independent positive integer, R 1 Each independently selected from any one of hydrogen radical, carboxyl, hydroxyl, siloxy, ester radical and sulfonic radical, 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 structure 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 structure in which m is 2 to 4, n is 1 to 3, and a is 10 to 14.
According to the invention, preferably, the weight ratio of the first polyester polyol to the second polyester polyol is from 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 selected from at least one of 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 present invention, the above-mentioned substances are all commercially available.
According to the invention, preferably, in the step (1), the temperature of the hot melting treatment is 140-150 ℃, and specifically 140 ℃, 142 ℃, 144 ℃, 146 ℃, 148 ℃, 150 ℃ or any value between the foregoing values; the conditions of the dehydration treatment at least include: the vacuum degree is-0.095 MPa to-0.1 MPa, and specifically can be-0.095 MPa, -0.096MPa, -0.097MPa, -0.098MPa, -0.099MPa, -0.1MPa or any value between the above values; the time is 1-2h, and specifically can be 1h, 1.5h, 2h or any value between the above values; the stirring speed is 150-200rpm, specifically 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm or any value between the above values.
According to the present invention, preferably, in step (2), the conditions of the mixing reaction include: the nitrogen protection is carried out, the vacuum degree is-0.095 MPa to-0.1 MPa, and specifically can be-0.095 MPa, -0.096MPa, -0.097MPa, -0.098MPa, -0.099MPa, -0.1MPa or any value between the above values; the temperature is 80-120 deg.C, specifically 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C or any value between the above values; the stirring speed is 150-200rpm, specifically 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm or any value between the above values.
According to the present invention, preferably, in the step (2), the condition that the mixing reaction process is finished at least satisfies: the isocyanate content in the product amounts to 1.8-2.2% by weight.
According to the invention, the isocyanate content of the product is determined in accordance with HG/T2409-92.
According to a particularly preferred embodiment of the present invention, the process for preparing moisture-curing polyurethane hotmelt adhesives comprises the following steps:
(1) Mixing a polyester polyol composition, tackifying resin and an additive, performing hot melting treatment at the temperature of 140-150 ℃, and performing dehydration treatment under the conditions that the vacuum degree is-0.095 MPa to-0.1 MPa and the stirring speed is 150-200rpm for 1-2h to obtain a treatment solution;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, carrying out mixed reaction under the conditions that the vacuum degree is-0.095 MPa to-0.1 MPa, the temperature is 80-120 ℃, and the stirring speed is 150-200rpm until the mass percentage content of the isocyanate in the product reaches 1.8-2.2%, and stopping the reaction;
the dosage of each raw material is as follows according to the weight portion: 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 each independently:
wherein m in the first polyester polyol and the second polyester polyol is different positive integers, n is respectively independent positive integers, a is different positive integers, and R is 1 Each independently selected from any one of hydrogen radical, carboxyl, hydroxyl, siloxy, ester radical and sulfonic radical, 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 structural formula of the first polyester polyol is shown in the specification, wherein m is 3-5, n is 1-3, and a is 6-10; the structural formula of the second polyester polyol is shown in the specification, wherein 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 2-18:1; the weight ratio of the total dosage of the first polyester polyol and the second polyester polyol to the total dosage of the amorphous polyester polyol and the liquid polyester polyol is 2.25-11:1.
in the above particularly preferred embodiment, the preparation method of the moisture-curable 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 below by way of examples.
The reagents involved in the examples and comparative examples of the present invention are illustrated below:
in the following examples, the first polyester polyol is available from Asahi Sichuan chemical company, inc. under the types XCP-2000IPS, XCP-2000PM, XCP-PA110N; the second polyester polyol is obtained from Asahi Chun chemical company, suzhou, with the types XCP-3000N, XCP-3000H, XCPA-195; the amorphous polyester polyol is purchased from Yingchuang specialty Chemicals (Shanghai) Co., ltd, and has the model number Dynacoll-7130; the liquid polyester polyol is purchased from Yingchuang specialty Chemicals (Shanghai) Co., ltd, and has the model of Dynacoll-7250; the crystalline polyester polyol is available from Asahi Chun chemical company, suzhou, inc., and has models of XCP-44 and XCP-3000B; the modified rosin resin is purchased from Shenzhen Quanying chemical Co., ltd, and has the model of YH-100C; isocyanate was purchased from basf polyurethane (Chongqing) Inc. and has a model number MS-C; the light stabilizer is purchased from North City chemical industry Co., ltd, and the model is JF-90; the antioxidant is purchased from New Tianjin Lianlong Material Co., ltd, and has a model of RIAOX 1010; one commercially available moisture-curable polyurethane hot melt adhesive is available from Asahi Chun chemical, inc. under the model number XCUR-6018.
In the following examples, 1 part by weight represents 1g.
Example 1
(1) Mixing first polyester polyol, second polyester polyol, amorphous polyester polyol, liquid polyester polyol, modified rosin resin, a light stabilizer and an antioxidant, performing hot melting treatment at the temperature of 145 ℃, and performing dehydration treatment under the conditions of vacuum degree of-0.098 MPa and stirring speed of 175rpm for 1.5 hours to obtain a treatment solution;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, carrying out mixing reaction under the conditions of vacuum degree of-0.098 MPa, temperature of 100 ℃ and stirring speed of 175rpm until the mass percentage content of the isocyanate in the product reaches 2.0%, and stopping the reaction;
the dosage of each raw material is as follows according to the weight portion: 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);
wherein R in the structural formula of the first polyester polyol 1 Is a phthalic anhydride group, R 2 Is a hydroxyl group, m =4, n =2, a =8, xcp-2000IPS (hydroxyl value 53-59 mgKOH/g), molecular weight about 2000; r in the second polyester polyol formula 1 Is a phthalic anhydride group, R 2 M =3, N =2, a =12, model XCP-3000N (hydroxyl value 35-39 mgKOH/g), molecular weight about 3000, for hydroxyl groups.
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 the temperature of 150 ℃, and performing dehydration treatment under the conditions of a vacuum degree of-0.1 MPa and a stirring frequency of 200rpm for 1h to obtain a treatment solution;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, carrying out mixed reaction under the conditions of vacuum degree of-0.1 MPa, temperature of 80 ℃ and stirring frequency of 200rpm until the mass percentage content of the isocyanate in the product reaches 1.8%, and stopping the reaction;
the dosage of each raw material is as follows according to the weight portion: 30 parts of first polyester polyol (XCP-2000 IPS), 15 parts of second polyester polyol (XCP-3000N), 10 parts of amorphous polyester polyol (Dynacoll-7130), 10 parts of liquid polyester polyol (Dynacoll-7250), 5 parts of modified rosin resin (YH-100C), 10 parts of isocyanate (MS-C), 0.1 part of light stabilizer (JF-90) and 0.1 part of 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 the temperature of 140 ℃, and performing dehydration treatment under the conditions of a vacuum degree of-0.095 MPa and a stirring rotation speed of 150rpm for 2 hours to obtain a treatment solution;
(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, temperature of 120 ℃ and stirring speed of 150rpm until the mass percentage content of the isocyanate in the product reaches 2.2 percent, and stopping the reaction;
the dosage of each raw material is as follows according to the weight portion: first polyester polyol type (XCP-2000 PM)
90 parts, 5 parts of second polyester polyol (model XCP-3000H), 4.3 parts of amorphous polyester polyol (Dynacoll-7130), 4.3 parts of liquid polyester polyol (Dynacoll-7250), 10 parts of modified rosin resin (YH-100C), 25 parts of isocyanate (MS-C), 0.5 part of light stabilizer (JF-90) and 0.5 part of antioxidant (RIANOX 1010);
wherein R in the structural formula of the first polyester polyol 1 Is a phthalic anhydride group, R 2 Is hydroxyl, m =5,n =3,a =7, model XCP-2000PM (hydroxyl value 53-59 mgKOH/g), molecular weight is about 2000; r in the second polyester polyol formula 1 Is a phthalic anhydride group, R 2 Is hydroxyl, m =2,n =2,a =14, model XCP-3000H (hydroxyl value 34-40 mgKOH/g), and molecular weight is about 3000.
Example 4
A moisture-curing polyurethane hot melt adhesive was prepared according to the method of example 1, except that the raw materials were used in the following amounts by weight: 70 parts of first polyester polyol (model XCP-PA 110N), 10 parts of second polyester polyol (model XCPA-195), 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);
wherein R in the structural formula of the first polyester polyol 1 Is a phthalic anhydride group, R 2 Is hydroxyl, m =8, N =4, a =3, model XCP-PA110N (hydroxyl value 104-110 mgKOH/g), molecular weight is about 1000; r in the second polyester polyol formula 1 Is a phthalic anhydride group, R 2 M =5, n =4, a =2, model XCPA-195 (hydroxyl value 190-205 mgKOH/g), molecular weight is about 560.
Example 5
A moisture-curing polyurethane hot melt adhesive was prepared according to the method of example 1, except that the raw materials were used in the following amounts by weight: 40 parts of first polyester polyol (XCP-2000 IPS), 40 parts of second polyester polyol (XCP-3000N), 20 parts of amorphous polyester polyol (Dynacoll-7130), 20 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).
Example 6
A moisture-curing polyurethane hot melt adhesive was prepared according to the method of example 1, except that the raw materials were used in the following amounts 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, a light stabilizer and an antioxidant, performing hot melting treatment at the temperature of 145 ℃, and performing dehydration treatment under the conditions of vacuum degree of-0.098 MPa and stirring speed of 175rpm for 1.5h to obtain a treatment solution;
(2) Under the protection of nitrogen, adding isocyanate into the treatment liquid, carrying out mixing reaction under the conditions of vacuum degree of-0.098 MPa, temperature of 100 ℃ and stirring speed of 175rpm until the mass percentage content of the isocyanate in the product reaches 2.0%, and stopping the reaction;
the dosage of each raw material is as follows according to the weight portion: 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 a first polyester polyol, a second polyester polyol, an amorphous polyester polyol, a liquid polyester polyol, isocyanate, a modified rosin resin, a light stabilizer and an antioxidant, performing hot melting treatment at the temperature of 145 ℃, performing dehydration treatment under the conditions of vacuum degree of-0.098 MPa and stirring frequency of 75Hz until the mass percentage content of the isocyanate in the product reaches 2.0%, and stopping reaction;
the dosage of each raw material is as follows according to the weight portion: 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
Certain commercially available moisture-curing polyurethane hotmelt adhesives (XCUR-6018).
Test example
The moisture-curable polyurethane hot melt adhesives prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to viscosity, open time, initial peel strength and final peel strength tests, and the results are shown in Table 1.
The moisture-curable polyurethane hot melt adhesives prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to a PVC film/wood plastic panel adhesion test, and the results are shown in table 2.
TABLE 1
TABLE 2
As can be seen from the results in tables 1 and 2, the moisture-curable polyurethane hot melt adhesives obtained in examples 1 to 6 by using the preparation method provided by the present invention have better initial peel strength and higher final peel strength, and the adhesive effect is significantly improved compared to comparative examples 1 to 3.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
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.
2. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the polyester polyol composition comprises a first polyester polyol and a second polyester polyol, each of the first polyester polyol and the second polyester polyol independently having the structural formula:
wherein m in the first polyester polyol and the second polyester polyol is different positive integers, n is respectively independent positive integer, a is respectively independent positive integer, R 1 Each independently selected from any one of hydrogen radical, carboxyl, hydroxyl, siloxy, ester radical and sulfonic radical, 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.
3. The moisture-curable polyurethane hot melt adhesive according to claim 2, wherein the first polyester polyol has a structural formula in which m is 3 to 5, n is 1 to 3, a is 6 to 10;
preferably, the second polyester polyol has a structure wherein m is 2 to 4, n is 1 to 3, 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.
4. the moisture-curable polyurethane hot melt adhesive according to claim 2, wherein the polyester polyol composition further comprises an auxiliary polyester polyol;
preferably, the auxiliary polyester polyol is amorphous polyester polyol and/or 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 from 2.25 to 11:1.
5. the moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 4, wherein the tackifying resin is selected from at least one of C5 petroleum resins, C9 petroleum resins, hydrogenated petroleum resins, modified rosin resins and rosins;
preferably, the isocyanate is selected from at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylm-xylylene diisocyanate, and isophorone diisocyanate;
preferably, the additive is selected from at least one of a light stabilizer, an antioxidant, and a metal deactivator.
6. A preparation method of a moisture-curing polyurethane hot melt adhesive is characterized by comprising the following steps:
(1) Mixing the polyester polyol composition, tackifying resin and additive, and then carrying out hot melting treatment and dehydration treatment to obtain a treatment solution;
(2) Mixing the treatment liquid with isocyanate for reaction;
wherein the dosage of each raw material is as follows according to the weight portion: 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.
7. The method of claim 6, wherein the polyester polyol composition comprises a first polyester polyol and a second polyester polyol, each of the first polyester polyol and the second polyester polyol independently having the structural formula:
wherein m in the first polyester polyol and the second polyester polyol is different positive integers, n is respectively independent positive integer, a is respectively independent positive integer, R 1 Each independently selected from any one of hydrogen radical, carboxyl, hydroxyl, siloxy, ester radical and sulfonic radical, R 2 Each independently selected from any one of a siloxy group, a carboxyl group, an ester group, a hydroxyl group and a sulfonic group;
preferably, the first polyester polyol has a structure in which m is 3 to 5, n is 1 to 3, a is 6 to 10;
preferably, the second polyester polyol has a structure wherein m is 2 to 4, n is 1 to 3, 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 amorphous polyester polyol and/or 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 from 2.25 to 11:1.
8. the production method according to claim 6, wherein the tackifier resin is at least one selected from the group consisting of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, modified rosin resin and rosin;
preferably, the isocyanate is selected from at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylm-xylylene diisocyanate, and isophorone diisocyanate;
preferably, the additive is selected from at least one of a light stabilizer, an antioxidant and a metal deactivator.
9. The production method according to any one of claims 6 to 8, wherein in the step (1), the hot-melt treatment is carried out at a temperature of 140 to 150 ℃;
the conditions of the dehydration treatment at least include: the vacuum degree is between-0.095 MPa and-0.1 MPa, the time is 1 to 2 hours, and the stirring speed is 150 to 200rpm.
10. The production method according to any one of claims 6 to 8, wherein in the step (2), the conditions of the mixing reaction include at least: under the protection of nitrogen, the vacuum degree is between-0.095 MPa and-0.1 MPa, the temperature is between 80 and 120 ℃, and the stirring speed is between 150 and 200rpm;
preferably, in the step (2), the condition for ending the mixing reaction process at least satisfies: the isocyanate content in the product amounts to 1.8-2.2% by weight.
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| 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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| 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 |
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