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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- 239000004831 Hot glue Substances 0.000 title claims abstract description 42
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 238000013008 moisture curing Methods 0.000 title claims abstract description 32
- 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 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 47
- 239000012948 isocyanate Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 35
- 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 24
- 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 24
- 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 24
- 239000003963 antioxidant agent Substances 0.000 claims description 22
- 239000004611 light stabiliser Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 208000005156 Dehydration Diseases 0.000 claims description 17
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 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
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 15
- 239000012943 hotmelt Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 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
- 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
- 239000002184 metal Substances 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
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 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 3
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 238000003303 reheating Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 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
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 125000000542 sulfonic acid group Chemical group 0.000 description 10
- 238000000034 method Methods 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 7
- 238000000576 coating method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229930193351 phorone Natural products 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明涉及热熔胶制备领域，公开了一种湿固化聚氨酯热熔胶及其制备方法。本发明提供的一种湿固化聚氨酯热熔胶，含有以下重量份组成的原料：聚酯多元醇组合物55‑130份，增粘树脂5‑10份，异氰酸酯10‑25份，添加剂0.2‑1份。通过本发明制备所得的湿固化聚氨酯热熔胶，在低温环境(25℃及以下)中包覆样件时，不需要对基材加热或者样件回热而直接进行粘结，有助于减少生产成本，并提高经济效益。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 contains the following raw materials by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate, and 0.2-1 additive. share. The moisture-curing polyurethane hot melt adhesive prepared by the present invention can be directly bonded without heating the base material or reheating the sample when covering the sample in a low-temperature environment (25°C and below), which helps to reduce production costs and improve economic efficiency.
Description
技术领域Technical field
本发明涉及热熔胶制备领域，具体涉及一种湿固化聚氨酯热熔胶及其制备方法。The invention relates to the field of hot melt adhesive preparation, and in particular to a moisture-curing polyurethane hot melt adhesive and a preparation method thereof.
背景技术Background technique
湿固化聚氨酯热熔胶是一种由含有异氰酸酯官能团封端的聚氨酯预聚体与多种助剂混合而成的胶黏剂，不含水和溶剂，固含量为100％，是一种高性能环保型胶黏剂，符合国内越来越严格的环境政策和需求。湿固化聚氨酯热熔胶是具有高粘结强度的交联型结构胶，可以快速定位、快速固化，初粘力比较强，又具有反应型胶粘剂特有的耐水、耐热、耐寒、耐蠕变和耐介质等性能。Moisture-curing polyurethane hot melt adhesive is an adhesive that is mixed with a polyurethane prepolymer containing isocyanate functional groups and a variety of additives. It does not contain water and solvents and has a solid content of 100%. It is a high-performance and environmentally friendly adhesive. Adhesives comply with increasingly stringent domestic environmental policies and demands. Moisture-curing polyurethane hot melt adhesive is a cross-linked structural adhesive with high bonding strength. It can be positioned quickly, cured quickly, has relatively strong initial adhesion, and has the unique water resistance, heat resistance, cold resistance, creep resistance and resistance of reactive adhesives. Media resistance and other properties.
现有的中国专利(CN107488430A)公开了一种用于家具及装饰构件异形面包覆的湿固化聚氨酯热熔胶。该专利提供了一种用于家具及装饰构件异形面包覆的湿固化聚氨酯热熔胶，整个湿固化聚氨酯热熔胶表现出初始剥离强度和最终剥离强度高的优点，流动性好，定位能力强。但该包覆胶由于添加较多强结晶性聚酯多元醇，虽可在前期提供较强的粘合能力，但在低温环境(25℃及以下)中包覆样件时，需要额外增加加热装置对包覆基材进行加热或者在包覆完成后对样件进行回热，这样才能满足对PVC膜或者基材的良好粘接，如此一来，增加了包覆工艺的调机难度和加热装置的配置成本。The existing Chinese patent (CN107488430A) discloses a moisture-curing polyurethane hot melt adhesive used for covering special-shaped surfaces of furniture and decorative components. This patent provides a moisture-curing polyurethane hot-melt adhesive for covering special-shaped surfaces of furniture and decorative components. The entire moisture-curing polyurethane hot-melt adhesive exhibits the advantages of high initial peel strength and final peel strength, good fluidity, and positioning ability. powerful. However, due to the addition of more strong crystalline polyester polyol, this coating glue can provide strong adhesion ability in the early stage, but when coating samples in low temperature environments (25°C and below), additional heating is required. The device heats the coating base material or reheats the sample after the coating is completed, so as to achieve good adhesion to the PVC film or base material. This increases the difficulty of adjusting the coating process and heating. Configuration cost of the device.
发明内容Contents of the invention
本发明的目的是为了克服现有技术存在的问题，提供一种湿固化聚氨酯热熔胶及其制备方法，通过独特的原料配比及合成，使通过本发明制备所得的湿固化聚氨酯热熔胶的初粘强度和终粘强度高，具有较好的流动性和快速定位的效果，还可以在低温环境中不需要对基材加热或者样件回热而直接进行粘结，有助于减少生产成本，并提高经济效益。The purpose of the present invention is to overcome the problems existing in the prior art and provide a moisture-curing polyurethane hot-melt adhesive and a preparation method thereof. Through a unique raw material ratio and synthesis, the moisture-curing polyurethane hot-melt adhesive prepared by the present invention can It has high initial and final bonding strengths, good fluidity and rapid positioning effect. It can also be bonded directly in low temperature environments without heating the substrate or reheating the sample, which helps reduce production costs and improve economic efficiency.
为了实现上述目的，本发明是通过以下技术方案获得的。In order to achieve the above objects, the present invention is obtained through the following technical solutions.
本发明第一方面提供一种湿固化聚氨酯热熔胶，含有以下重量份组成的原料：聚酯多元醇组合物55-130份，增粘树脂5-10份，异氰酸酯10-25份，添加剂0.2-1份。The first aspect of the invention provides a moisture-curing polyurethane hot melt adhesive, which contains the following raw materials by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate, and 0.2 parts of additives -1 serving.
优选地，所述聚酯多元醇组合物含有第一聚酯多元醇和第二聚酯多元醇，所述第一聚酯多元醇和所述第二聚酯多元醇的结构式分别独立地为：Preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, and the structural formulas of the first polyester polyol and the second polyester polyol are independently:
其中，所述第一聚酯多元醇和所述第二聚酯多元醇中的m为不同的正整数，n为分别独立的正整数，a为分别独立的正整数，R1分别独立地选自氢基、羧基、羟基、硅氧基、酯基和磺酸基中的任意一种，R2分别独立地选自硅氧基、羧基、酯基、羟基和磺酸基中的任意一种。Wherein, m in the first polyester polyol and the second polyester polyol are different positive integers, n is an independent positive integer, a is an independent positive integer, and R 1 is independently selected from Any one of hydrogen group, carboxyl group, hydroxyl group, siloxy group, ester group and sulfonic acid group, R2 is independently selected from any one of siloxy group, carboxyl group, ester group, hydroxyl group and sulfonic acid group.
优选地，所述第一聚酯多元醇的结构式中m为3-5，n为1-3，a为6-10；Preferably, in the structural formula of the first polyester polyol, m is 3-5, n is 1-3, and a is 6-10;
优选地，所述第二聚酯多元醇的结构式中m为2-4，n为1-3，a为10-14；Preferably, in the structural formula of the second polyester polyol, m is 2-4, n is 1-3, and a is 10-14;
优选地，所述第一聚酯多元醇与所述第二聚酯多元醇的重量比为2-18：1。Preferably, the weight ratio of the first polyester polyol to the second polyester polyol is 2-18:1.
优选地，所述聚酯多元醇组合物还含有辅助聚酯多元醇；Preferably, the polyester polyol composition further contains an auxiliary polyester polyol;
优选地，所述辅助聚酯多元醇为无定型聚酯多元醇和/或液态聚酯多元醇；Preferably, the auxiliary polyester polyol is amorphous polyester polyol and/or liquid polyester polyol;
优选地，所述第一聚酯多元醇和所述第二聚酯多元醇的总用量与所述辅助聚酯多元醇的重量比为2.25-11：1。Preferably, the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the auxiliary polyester polyol is 2.25-11:1.
优选地，所述增粘树脂选自C5石油树脂、C9石油树脂、氢化石油树脂、改性松香树脂和松香中的至少一种；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;
优选地，所述异氰酸酯选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和异佛尔酮二异氰酸酯中的至少一种；Preferably, the isocyanate is selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylisoxylylene diisocyanate and isophorone diisocyanate. at least one of isocyanates;
优选地，所述添加剂选自光稳定剂、抗氧剂和金属钝化剂中的至少一种。Preferably, the additive is selected from at least one of light stabilizers, antioxidants and metal passivators.
本方面第二方面提供一种湿固化聚氨酯热熔胶的制备方法，包括如下步骤：A second aspect of this aspect provides a method for preparing moisture-cured polyurethane hot melt adhesive, which includes the following steps:
(1)将聚酯多元醇组合物、增粘树脂、添加剂混合后进行热熔处理和脱水处理，得到处理液；(1) Mix the polyester polyol composition, tackifying resin, and additives and then perform hot melt treatment and dehydration treatment to obtain a treatment liquid;
(2)将所述处理液与异氰酸酯进行混合反应；(2) Mix and react the treatment liquid with isocyanate;
其中，各原料的用量按照重量份计为：聚酯多元醇组合物55-130份，增粘树脂5-10份，异氰酸酯10-25份，添加剂0.2-1份。Among them, the amount of each raw material is calculated 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 additives.
优选地，所述聚酯多元醇组合物含有第一聚酯多元醇和第二聚酯多元醇，所述第一聚酯多元醇和所述第二聚酯多元醇的结构式分别独立地为：Preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, and the structural formulas of the first polyester polyol and the second polyester polyol are independently:
其中，所述第一聚酯多元醇和所述第二聚酯多元醇中的m为不同的正整数，n为分别独立的正整数，a为分别独立的正整数，R1分别独立地选自氢基、羧基、羟基、硅氧基、酯基和磺酸基中的任意一种，R2分别独立地选自硅氧基、羧基、酯基、羟基和磺酸基中的任意一种；Wherein, m in the first polyester polyol and the second polyester polyol are different positive integers, n is an independent positive integer, a is an independent positive integer, and R 1 is independently selected from Any one of hydrogen group, carboxyl group, hydroxyl group, siloxy group, ester group and sulfonic acid group, R2 is independently selected from any one of siloxy group, carboxyl group, ester group, hydroxyl group and sulfonic acid group;
优选地，所述第一聚酯多元醇的结构式中m为3-5，n为1-3，a为6-10；Preferably, in the structural formula of the first polyester polyol, m is 3-5, n is 1-3, and a is 6-10;
优选地，所述第二聚酯多元醇的结构式中m为2-4，n为1-3，a为10-14；Preferably, in the structural formula of the second polyester polyol, m is 2-4, n is 1-3, and a is 10-14;
优选地，所述第一聚酯多元醇与所述第二聚酯多元醇的重量比为2-18：1；Preferably, the weight ratio of the first polyester polyol to the second polyester polyol is 2-18:1;
优选地，所述聚酯多元醇组合物还含有辅助聚酯多元醇；Preferably, the polyester polyol composition further contains an auxiliary polyester polyol;
优选地，所述辅助聚酯多元醇为无定型聚酯多元醇和/或液态聚酯多元醇；Preferably, the auxiliary polyester polyol is amorphous polyester polyol and/or liquid polyester polyol;
优选地，所述第一聚酯多元醇和所述第二聚酯多元醇的总用量与所述辅助聚酯多元醇的重量比为2.25-11：1。Preferably, the weight ratio of the total amount of the first polyester polyol and the second polyester polyol to the auxiliary polyester polyol is 2.25-11:1.
优选地，所述增粘树脂选自C5石油树脂、C9石油树脂、氢化石油树脂、改性松香树脂和松香中的至少一种；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;
优选地，所述异氰酸酯选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和异佛尔酮二异氰酸酯中的至少一种；Preferably, the isocyanate is selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylisoxylylene diisocyanate and isophorone diisocyanate. at least one of isocyanates;
优选地，所述添加剂选自光稳定剂、抗氧剂和金属钝化剂中的至少一种。Preferably, the additive is selected from at least one of light stabilizers, antioxidants and metal passivators.
优选地，在步骤(1)中，所述热熔处理在温度为140-150℃的条件下进行；Preferably, in step (1), the hot melt treatment is performed at a temperature of 140-150°C;
所述脱水处理的条件至少包括：真空度为-0.095MPa至-0.1MPa，时间为1-2h，搅拌转速为150-200rpm。The conditions for the dehydration treatment at least include: vacuum degree is -0.095MPa to -0.1MPa, time is 1-2h, and stirring speed is 150-200rpm.
优选地，在步骤(2)中，所述混合反应的条件至少包括：氮气保护，真空度为-0.095MPa至-0.1MPa，温度为80-120℃，搅拌转速为150-200rpm；Preferably, in step (2), the conditions for the mixed reaction at least include: nitrogen protection, vacuum degree of -0.095MPa to -0.1MPa, temperature of 80-120°C, and stirring speed of 150-200rpm;
优选地，在步骤(2)中，所述混合反应过程结束的条件至少满足：产物中异氰酸酯的含量达到1.8-2.2重量％。Preferably, in step (2), the conditions for the end of the mixing reaction process are at least satisfied: the isocyanate content in the product reaches 1.8-2.2% by weight.
通过上述技术方案，本发明的有益效果为：本发明提供的湿固化聚氨酯热熔胶及其制备方法，通过独特的原料配比及合成，使通过本发明制备所得的湿固化聚氨酯热熔胶的初粘强度和终粘强度高，具有较好的流动性和快速定位的效果。Through the above technical solutions, the beneficial effects of the present invention are: the moisture-curing polyurethane hot-melt adhesive and its preparation method provided by the invention, through unique raw material ratio and synthesis, make the moisture-curing polyurethane hot-melt adhesive prepared by the invention more It has high initial and final bonding strength, good fluidity and rapid positioning effect.
进一步地，本发明提供的湿固化聚氨酯热熔胶及其制备方法，通过对第一聚酯多元醇和第二聚酯多元醇的分子结构设计，将特殊的基团引入主碳链，控制聚酯多元醇组合物的分子量，并通过第一聚酯多元醇和第二聚酯多元醇的配合使用，解决在低温环境中包覆时需要对基材加热或对样件回热的问题，节约能源及成本。Furthermore, in the moisture-curing polyurethane hot melt adhesive and its preparation method provided by the present invention, through the molecular structure design of the first polyester polyol and the second polyester polyol, special groups are introduced into the main carbon chain to control the polyester The molecular weight of the polyol composition, and through the combined use of the first polyester polyol and the second polyester polyol, solve the problem of heating the substrate or reheating the sample when coating in a low-temperature environment, saving energy and cost.
具体实施方式Detailed ways
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope shall be deemed to be specifically disclosed herein.
本发明第一方面提供了一种湿固化聚氨酯热熔胶，含有以下重量份组成的原料：聚酯多元醇组合物55-130份，增粘树脂5-10份，异氰酸酯10-25份，添加剂0.2-1份。The first aspect of the invention provides a moisture-curing polyurethane hot melt adhesive, which contains the following raw materials by weight: 55-130 parts of polyester polyol composition, 5-10 parts of tackifying resin, 10-25 parts of isocyanate, and additives 0.2-1 serving.
根据本发明，优选地，所述聚酯多元醇组合物含有第一聚酯多元醇和第二聚酯多元醇，所述第一聚酯多元醇和所述第二聚酯多元醇的结构式分别独立地为：According to the present invention, preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, and the structural formulas of the first polyester polyol and the second polyester polyol are independently for:
其中，所述第一聚酯多元醇和所述第二聚酯多元醇中的m为不同的正整数，n为分别独立的正整数，a为分别独立的正整数，R1分别独立地选自氢基、羧基、羟基、硅氧基、酯基和磺酸基中的任意一种，R2分别独立地选自硅氧基、羧基、酯基、羟基和磺酸基中的任意一种。第一聚酯多元醇和第二聚酯多元醇中的n可以相同，也可以不同，R1可以相同，也可以不同，R2可以相同，也可以不同，a可以相同，也可以不同。具体地，酯基是羧酸衍生物中酯的官能团，优选为苯酐基。Wherein, m in the first polyester polyol and the second polyester polyol are different positive integers, n is an independent positive integer, a is an independent positive integer, and R 1 is independently selected from Any one of hydrogen group, carboxyl group, hydroxyl group, siloxy group, ester group and sulfonic acid group, R2 is independently selected from any one of siloxy group, carboxyl group, ester group, hydroxyl group and 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 the functional group of the ester in the carboxylic acid derivative, and is preferably a phthalic anhydride group.
根据本发明，第一聚酯多元醇和第二聚酯多元醇可以直接市购获得，也可以通过现有技术中已公开的制备方法制得。According to the present invention, the first polyester polyol and the second polyester polyol can be directly purchased from the market, or can be prepared by preparation methods disclosed in the prior art.
根据本发明，优选地，所述第一聚酯多元醇的结构式中m为3-5，n为1-3，a为6-10。According to the present invention, preferably, in the structural formula of the first polyester polyol, m is 3-5, n is 1-3, and a is 6-10.
根据本发明，优选地，所述第二聚酯多元醇的结构式中m为2-4，n为1-3，a为10-14。According to the present invention, preferably, in the structural formula of the second polyester polyol, m is 2-4, n is 1-3, and a is 10-14.
根据本发明，优选地，所述第一聚酯多元醇与所述第二聚酯多元醇的重量比为2-18：1。发明人发现在该优选实施方式下，有助于提高湿固化聚氨酯热熔胶的初粘强度和终粘强度，流动性好，定位能力强。According to the present invention, preferably, the weight ratio of the first polyester polyol to the second polyester polyol is 2-18:1. The inventor found that this preferred embodiment is helpful to improve the initial bonding strength and final bonding strength of moisture-cured polyurethane hot melt adhesive, with good fluidity and strong positioning ability.
根据本发明，优选地，所述聚酯多元醇组合物还含有辅助聚酯多元醇。According to the present invention, preferably, the polyester polyol composition further contains an auxiliary polyester polyol.
根据本发明，优选地，所述辅助聚酯多元醇为无定型聚酯多元醇和/或液态聚酯多元醇。具体地，所述辅助聚酯多元醇为无定型聚酯多元醇和液态聚酯多元醇。无定型聚酯多元醇和液态聚酯多元醇可以直接市购获得，也可以通过现有技术中已公开的制备方法制得。例如，所述无定型聚酯多元醇可用的商品化产品有F-39030、F-37070、Dynacoll-7130、Dynacoll-7140等；所述液态聚酯多元醇可用的商品化产品有F-37030、XCP-2000IPS、Dynacoll-7250、Dynacoll-7230等。According to the present invention, preferably, the auxiliary polyester polyol is amorphous polyester polyol and/or liquid polyester polyol. Specifically, the auxiliary polyester polyol is amorphous polyester polyol and liquid polyester polyol. Amorphous polyester polyol and liquid polyester polyol can be purchased directly from the market, or can be prepared by preparation methods disclosed in the prior art. For example, the commercial products available for the amorphous polyester polyol include F-39030, F-37070, Dynacoll-7130, Dynacoll-7140, etc.; the commercial products available for the liquid polyester polyol include F-37030, XCP-2000IPS, Dynacoll-7250, Dynacoll-7230, etc.
根据本发明，优选地，所述第一聚酯多元醇和所述第二聚酯多元醇的总用量与所述辅助聚酯多元醇的重量比为2.25-11：1。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 2.25-11:1.
根据本发明，加入增粘树脂可以在湿固化聚氨酯热熔胶冷却时加速热熔胶凝聚，有利于提高湿固化聚氨酯热熔胶的初粘强度。优选地，所述增粘树脂选自C5石油树脂、C9石油树脂、氢化石油树脂、改性松香树脂和松香中的至少一种。更优选地，所述增粘树脂选自改性松香树脂，改性松香树脂可以商购得到，例如，可用的商品化产品有SNS-138、SNS-145、YH-100C等。According to the present invention, adding tackifying resin can accelerate the cohesion of the hot melt adhesive when the moisture-curing polyurethane hot-melt adhesive is cooled, which is beneficial to improving the initial bonding strength of the moisture-curing 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 modified rosin resins, which are commercially available. For example, available commercial products include SNS-138, SNS-145, YH-100C, etc.
根据本发明，优选地，所述异氰酸酯选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和异佛尔酮二异氰酸酯中的至少一种，这类异氰酸酯可以单独或组合使用，更优选地，所述异氰酸酯为二苯基甲烷二异氰酸酯。According to the present invention, preferably, the isocyanate is selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylisoxylylenediisocyanate and isocyanate. At least one of the phorone diisocyanates. Such isocyanates can be used alone or in combination. More preferably, the isocyanate is diphenylmethane diisocyanate.
根据本发明，加入添加剂可以提高湿固化聚氨酯热熔胶的耐热性，调节粘接强度，减少收缩，防止自粘，还可以降低成本。优选地，所述添加剂选自光稳定剂、抗氧剂和金属钝化剂中至少一种，更优选为光稳定剂和抗氧剂。光稳定剂和抗氧剂均可以商购得到，例如，所述抗氧剂可用的商品化产品有1076、1010、264、2246等；所述光稳定剂为光屏蔽剂、紫外线吸收剂、淬灭剂、自由基捕获剂和氢过氧化物分解剂中的一种或多种，可用的商品化产品有AM-101、GW-540、JF-90、HPT等。According to the present invention, adding additives can improve the heat resistance of moisture-cured polyurethane hot melt adhesive, adjust the bonding strength, reduce shrinkage, prevent self-adhesion, and also reduce costs. Preferably, the additive is selected from at least one of light stabilizers, antioxidants and metal passivators, more preferably light stabilizers and antioxidants. Both light stabilizers and antioxidants are commercially available. For example, the commercial products available for the antioxidants include 1076, 1010, 264, 2246, etc.; the light stabilizers are light shielding agents, ultraviolet absorbers, quenching agents, etc. One or more of the following: extinguisher, free radical scavenger and hydroperoxide decomposer. Available commercial products include AM-101, GW-540, JF-90, HPT, etc.
本发明第二方面提供一种湿固化聚氨酯热熔胶的制备方法，包括如下步骤：A second aspect of the invention provides a method for preparing moisture-curing polyurethane hot melt adhesive, which includes the following steps:
(1)将聚酯多元醇组合物、增粘树脂、添加剂混合后进行热熔处理和脱水处理，得到处理液；(1) Mix the polyester polyol composition, tackifying resin, and additives and then perform hot melt treatment and dehydration treatment to obtain a treatment liquid;
(2)将所述处理液与异氰酸酯进行混合反应；(2) Mix and react the treatment liquid with isocyanate;
其中，各原料的用量按照重量份计为：聚酯多元醇组合物55-130份，增粘树脂5-10份，异氰酸酯10-25份，添加剂0.2-1份。Among them, the amount of each raw material is calculated 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 additives.
根据本发明，优选地，所述聚酯多元醇组合物含有第一聚酯多元醇和第二聚酯多元醇，所述第一聚酯多元醇和所述第二聚酯多元醇的结构式分别独立地为：According to the present invention, preferably, the polyester polyol composition contains a first polyester polyol and a second polyester polyol, and the structural formulas of the first polyester polyol and the second polyester polyol are independently for:
其中，所述第一聚酯多元醇和所述第二聚酯多元醇中的m为不同的正整数，n为分别独立的正整数，a为分别独立的正整数，R1分别独立地选自氢基、羧基、羟基、硅氧基、酯基和磺酸基中的任意一种，R2分别独立地选自硅氧基、羧基、酯基、羟基和磺酸基中的任意一种。Wherein, m in the first polyester polyol and the second polyester polyol are different positive integers, n is an independent positive integer, a is an independent positive integer, and R 1 is independently selected from Any one of hydrogen group, carboxyl group, hydroxyl group, siloxy group, ester group and sulfonic acid group, R2 is independently selected from any one of siloxy group, carboxyl group, ester group, hydroxyl group and sulfonic acid group.
根据本发明，优选地，所述第一聚酯多元醇的结构式中m为3-5，n为1-3，a为6-10。According to the present invention, preferably, in the structural formula of the first polyester polyol, m is 3-5, n is 1-3, and a is 6-10.
根据本发明，优选地，所述第二聚酯多元醇的结构式中m为2-4，n为1-3，a为10-14。According to the present invention, preferably, in the structural formula of the second polyester polyol, m is 2-4, n is 1-3, and a is 10-14.
根据本发明，优选地，所述第一聚酯多元醇与所述第二聚酯多元醇的重量比为2-18：1。According to the present invention, preferably, the weight ratio of the first polyester polyol to the second polyester polyol is 2-18:1.
根据本发明，优选地，所述聚酯多元醇组合物还含有辅助聚酯多元醇。According to the present invention, preferably, the polyester polyol composition further contains an auxiliary polyester polyol.
根据本发明，优选地，所述辅助聚酯多元醇为无定型聚酯多元醇和/或液态聚酯多元醇。According to the present invention, preferably, the auxiliary polyester polyol is amorphous polyester polyol and/or liquid polyester polyol.
根据本发明，优选地，所述第一聚酯多元醇和所述第二聚酯多元醇的总用量与所述辅助聚酯多元醇的重量比为2.25-11：1。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 2.25-11:1.
根据本发明，优选地，所述增粘树脂选自C5石油树脂、C9石油树脂、氢化石油树脂、改性松香树脂和松香中的至少一种。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.
根据本发明，优选地，所述异氰酸酯选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和异佛尔酮二异氰酸酯中的至少一种。According to the present invention, preferably, the isocyanate is selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylisoxylylenediisocyanate and isocyanate. At least one kind of phorone diisocyanate.
根据本发明，优选地，所述添加剂选自光稳定剂、抗氧剂和金属钝化剂中的至少一种。According to the present invention, preferably, the additive is selected from at least one of a light stabilizer, an antioxidant and a metal passivator.
根据本发明，上述物质均可以通过商购获得。According to the present invention, the above-mentioned substances can be obtained commercially.
根据本发明，优选地，在步骤(1)中，所述热熔处理的温度为140-150℃，具体可以为140℃、142℃、144℃、146℃、148℃、150℃或前述数值之间的任意值；所述脱水处理的条件至少包括：真空度为-0.095MPa至-0.1MPa，具体可以为-0.095MPa、-0.096MPa、-0.097MPa、-0.098MPa、-0.099MPa、-0.1MPa或前述数值之间的任意值；时间为1-2h，具体可以为1h、1.5h、2h或前述数值之间的任意值；搅拌转速为150-200rpm，具体可以为150rpm、160rpm、170rpm、180rpm、190rpm、200rpm或前述数值之间的任意值。According to the present invention, preferably, in step (1), the temperature of the hot melt treatment is 140-150°C, specifically it can be 140°C, 142°C, 144°C, 146°C, 148°C, 150°C or the aforementioned values. Any value between; the conditions for the dehydration treatment at least include: vacuum degree is -0.095MPa to -0.1MPa, specifically -0.095MPa, -0.096MPa, -0.097MPa, -0.098MPa, -0.099MPa, - 0.1MPa or any value between the aforementioned values; the time is 1-2h, specifically it can be 1h, 1.5h, 2h or any value between the aforementioned values; the stirring speed is 150-200rpm, specifically it can be 150rpm, 160rpm, 170rpm , 180rpm, 190rpm, 200rpm or any value between the aforementioned values.
根据本发明，优选地，在步骤(2)中，所述混合反应的条件包括：氮气保护，真空度为-0.095MPa至-0.1MPa，具体可以为-0.095MPa、-0.096MPa、-0.097MPa、-0.098MPa、-0.099MPa、-0.1MPa或前述数值之间的任意值；温度为80-120℃，具体可以为80℃、90℃、100℃、110℃、120℃或前述数值之间的任意值；搅拌转速为150-200rpm，具体可以为150rpm、160rpm、170rpm、180rpm、190rpm、200rpm或前述数值之间的任意值。According to the present invention, preferably, in step (2), the conditions of the mixed reaction include: nitrogen protection, vacuum degree is -0.095MPa to -0.1MPa, specifically -0.095MPa, -0.096MPa, -0.097MPa , -0.098MPa, -0.099MPa, -0.1MPa or any value between the aforementioned values; the temperature is 80-120℃, specifically it can be 80℃, 90℃, 100℃, 110℃, 120℃ or between the aforementioned values. Any value; the stirring speed is 150-200rpm, specifically it can be 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm or any value between the aforementioned values.
根据本发明，优选地，在步骤(2)中，所述混合反应过程结束的条件至少满足：产物中异氰酸酯的含量达到1.8-2.2重量％。According to the present invention, preferably, in step (2), the conditions for the end of the mixing reaction process at least meet: the isocyanate content in the product reaches 1.8-2.2% by weight.
根据本发明，产物中异氰酸酯含量的测定方法按照HG/T 2409-92进行。According to the present invention, the method for determining the isocyanate content in the product is carried out in accordance with HG/T 2409-92.
根据本发明一种特别优选的实施方式，湿固化聚氨酯热熔胶的制备方法包括以下步骤：According to a particularly preferred embodiment of the present invention, the preparation method of moisture-curing polyurethane hot melt adhesive includes the following steps:
(1)将聚酯多元醇组合物、增粘树脂、添加剂混合后在温度为140-150℃的条件下进行热熔处理，在真空度为-0.095MPa至-0.1MPa、搅拌转速为150-200rpm的条件下进行脱水处理，脱水时间为1-2h，得到处理液；(1) Mix the polyester polyol composition, tackifying resin, and additives and then perform hot melt treatment at a temperature of 140-150°C, a vacuum degree of -0.095MPa to -0.1MPa, and a stirring speed of 150- Carry out dehydration treatment under the condition of 200rpm, the dehydration time is 1-2h, and the treatment liquid is obtained;
(2)在氮气的保护下，将异氰酸酯加入所述处理液中，在真空度为-0.095MPa至-0.1MPa、温度为80-120℃、搅拌转速为150-200rpm的条件下进行混合反应，直至产物中异氰酸酯的质量百分含量达到1.8-2.2％，停止反应；(2) Under the protection of nitrogen, add isocyanate into the treatment liquid, and perform a mixing reaction under the conditions of a vacuum of -0.095MPa to -0.1MPa, a temperature of 80-120°C, and a stirring speed of 150-200rpm, Stop the reaction until the mass percentage of isocyanate in the product reaches 1.8-2.2%;
各原料的用量按照重量份计为：聚酯多元醇组合物55-130份，增粘树脂5-10份，异氰酸酯10-25份，添加剂0.2-1份；The dosage of each raw material is calculated 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 additives;
聚酯多元醇组合物含有第一聚酯多元醇、第二聚酯多元醇、无定型聚酯多元醇和液态聚酯多元醇；The polyester polyol composition contains a first polyester polyol, a second polyester polyol, an amorphous polyester polyol and a liquid polyester polyol;
第一聚酯多元醇和所述第二聚酯多元醇的结构式分别独立地为：The structural formulas of the first polyester polyol and the second polyester polyol are independently:
其中，所述第一聚酯多元醇和所述第二聚酯多元醇中的m为不同的正整数，n为分别独立的正整数，a为不同的正整数，R1分别独立地选自氢基、羧基、羟基、硅氧基、酯基和磺酸基中的任意一种，R2分别独立地选自硅氧基、羧基、酯基、羟基和磺酸基中的任意一种；Wherein, m in the first polyester polyol and the second polyester polyol are different positive integers, n is an independent positive integer, a is a different positive integer, and R1 is independently selected from hydrogen. any one of siloxy group, carboxyl group, hydroxyl group, siloxy group, ester group and sulfonic acid group, R 2 is independently selected from any one of siloxy group, carboxyl group, ester group, hydroxyl group and sulfonic acid group;
第一聚酯多元醇的结构式中m为3-5，n为1-3，a为6-10；第二聚酯多元醇的结构式中m为2-4，n为1-3，a为10-14；In the structural formula of the first polyester polyol, m is 3-5, n is 1-3, and a is 6-10; in the structural formula of the second polyester polyol, m is 2-4, n is 1-3, and a is 10-14;
第一聚酯多元醇与所述第二聚酯多元醇的重量比为2-18：1；第一聚酯多元醇、第二聚酯多元醇的总用量与无定型聚酯多元醇、液态聚酯多元醇的总用量的重量比为2.25-11：1。The weight ratio of the first polyester polyol to the second polyester polyol is 2-18:1; the total amount of the first polyester polyol and the second polyester polyol is the same as that of the amorphous polyester polyol and the liquid polyester polyol. The weight ratio of the total amount of polyester polyol is 2.25-11:1.
上述特别优选的实施方式中，湿固化聚氨酯热熔胶的制备方法具有工艺简洁、成本低的优点，并通过后期的脱水处理步骤，使得产品便于存储和运输，有效维持产品性能的稳定。In the above-mentioned particularly preferred embodiment, the preparation method of moisture-curing polyurethane hot melt adhesive has the advantages of simple process and low cost, and through the later dehydration treatment step, the product is easy to store and transport, and the stability of the product performance is effectively maintained.
以下将通过实施例对本发明进行详细描述。The present invention will be described in detail below through examples.
本发明各实施例和对比例涉及的试剂说明如下：The reagents involved in each embodiment and comparative example of the present invention are described as follows:
以下实施例中，第一聚酯多元醇购自旭川化学(苏州)有限公司，型号为XCP-2000IPS、XCP-2000PM、XCP-PA110N；第二聚酯多元醇购自旭川化学(苏州)有限公司，型号为XCP-3000N、XCP-3000H、XCPA-195；无定型聚酯多元醇购自赢创特种化学(上海)有限公司，型号为Dynacoll-7130；液态聚酯多元醇购自赢创特种化学(上海)有限公司，型号为Dynacoll-7250；结晶型聚酯多元醇购自旭川化学(苏州)有限公司，型号为XCP-44、XCP-3000B；改性松香树脂购自深圳群英化工有限公司，型号为YH-100C；异氰酸酯购自巴斯夫聚氨酯(重庆)有限公司，型号为MS-C；光稳定剂购自城北化学工业株式会社，型号为JF-90；抗氧剂购自天津利安隆新材料股份有限公司，型号为RIANOX 1010；某市售湿固化聚氨酯热熔胶购自旭川化学(苏州)有限公司，型号为XCUR-6018。In the following examples, the first polyester polyol was purchased from Asahikawa Chemical (Suzhou) Co., Ltd., and the models are XCP-2000IPS, XCP-2000PM, and XCP-PA110N; the second polyester polyol was purchased from Asahikawa Chemical (Suzhou) Co., Ltd. , model numbers are XCP-3000N, (Shanghai) Co., Ltd., model number is Dynacoll-7250; crystalline polyester polyol was purchased from Asahikawa Chemical (Suzhou) Co., Ltd., model number is XCP-44, XCP-3000B; modified rosin resin was purchased from Shenzhen Qunying Chemical Co., Ltd. The model is YH-100C; the isocyanate is purchased from BASF Polyurethane (Chongqing) Co., Ltd., the model is MS-C; the light stabilizer is purchased from Chengbei Chemical Industry Co., Ltd., the model is JF-90; the antioxidant is purchased from Tianjin Li'anlong New Materials Co., Ltd., the model is RIANOX 1010; a commercially available moisture-curing polyurethane hot melt adhesive was purchased from Asahikawa Chemical (Suzhou) Co., Ltd., the model is XCUR-6018.
以下实施例中，1重量份代表1g。In the following examples, 1 part by weight represents 1 g.
实施例1Example 1
(1)将第一聚酯多元醇、第二聚酯多元醇、无定型聚酯多元醇、液态聚酯多元醇、改性松香树脂、光稳定剂和抗氧剂混合后在温度为145℃的条件下进行热熔处理，在真空度为-0.098MPa、搅拌转速为175rpm的条件下进行脱水处理，脱水时间为1.5h，得到处理液；(1) Mix the first polyester polyol, the second polyester polyol, amorphous polyester polyol, liquid polyester polyol, modified rosin resin, light stabilizer and antioxidant at a temperature of 145°C Carry out hot melt treatment under the conditions of -0.098MPa vacuum degree and 175rpm stirring speed for dehydration treatment. The dehydration time is 1.5h to obtain the treatment liquid;
(2)在氮气的保护下，将异氰酸酯加入所述处理液中，在真空度为-0.098MPa、温度为100℃、搅拌转速为175rpm的条件下进行混合反应，直至产物中异氰酸酯的质量百分含量达到2.0％，停止反应；(2) Under the protection of nitrogen, add isocyanate into the treatment liquid, and carry out a mixing reaction under the conditions of a vacuum of -0.098MPa, a temperature of 100°C, and a stirring speed of 175rpm, until the mass percentage of isocyanate in the product is When the content reaches 2.0%, the reaction stops;
各原料的用量按照重量份计为：第一聚酯多元醇(XCP-2000IPS)70份，第二聚酯多元醇(XCP-3000N)10份，无定型聚酯多元醇(Dynacoll-7130)10份，液态聚酯多元醇(Dynacoll-7250)10份，改性松香树脂(YH-100C)6份，异氰酸酯(MS-C)13.5份，光稳定剂(JF-90)0.25份，抗氧剂(RIANOX1010)0.25份；The dosage of each raw material is calculated in parts by weight: 70 parts of the first polyester polyol (XCP-2000IPS), 10 parts of the second polyester polyol (XCP-3000N), 10 parts of the amorphous polyester polyol (Dynacoll-7130) parts, 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 parts of light stabilizer (JF-90), antioxidant (RIANOX1010)0.25 parts;
其中，第一聚酯多元醇结构式中R1为苯酐基，R2为羟基，m＝4，n＝2，a＝8，XCP-2000IPS(羟值53-59mgKOH/g)，分子量约为2000；第二聚酯多元醇结构式中R1为苯酐基，R2为羟基，m＝3，n＝2，a＝12，型号XCP-3000N(羟值35-39mgKOH/g)，分子量约为3000。Among them, in the first polyester polyol structural formula, R 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), and the molecular weight is about 2000 ; In the second polyester polyol structural formula, R 1 is a phthalic anhydride group, R 2 is a hydroxyl group, m=3, n=2, a=12, model XCP-3000N (hydroxyl value 35-39mgKOH/g), molecular weight is about 3000 .
实施例2Example 2
(1)将第一聚酯多元醇、第二聚酯多元醇、无定型聚酯多元醇、液态聚酯多元醇、改性松香树脂、光稳定剂和抗氧剂混合后在温度为150℃的条件下进行热熔处理，在真空度为-0.1MPa、搅拌频率为200rpm的条件下进行脱水处理，脱水时间为1h，得到处理液；(1) Mix the first polyester polyol, the second polyester polyol, amorphous polyester polyol, liquid polyester polyol, modified rosin resin, light stabilizer and antioxidant at a temperature of 150°C Carry out hot melt treatment under the conditions of -0.1MPa vacuum degree and 200rpm stirring frequency. Dehydration time is 1h to obtain the treatment liquid;
(2)在氮气的保护下，将异氰酸酯加入所述处理液中，在真空度为-0.1MPa、温度为80℃、搅拌频率为200rpm的条件下进行混合反应，直至产物中异氰酸酯的质量百分含量达到1.8％，停止反应；(2) Under the protection of nitrogen, add isocyanate to the treatment liquid, and perform a mixing reaction under the conditions of a vacuum of -0.1MPa, a temperature of 80°C, and a stirring frequency of 200 rpm, until the mass percentage of isocyanate in the product is When the content reaches 1.8%, the reaction stops;
各原料的用量按照重量份计为：第一聚酯多元醇(XCP-2000IPS)30份，第二聚酯多元醇(XCP-3000N)15份，无定型聚酯多元醇(Dynacoll-7130)10份，液态聚酯多元醇(Dynacoll-7250)10份，改性松香树脂(YH-100C)5份，异氰酸酯(MS-C)10份，光稳定剂(JF-90)0.1份，抗氧剂(RIANOX1010)0.1份。The amount of each raw material used is calculated in parts by weight: 30 parts of the first polyester polyol (XCP-2000IPS), 15 parts of the second polyester polyol (XCP-3000N), 10 parts of the amorphous polyester polyol (Dynacoll-7130) parts, 10 parts of liquid polyester polyol (Dynacoll-7250), 5 parts of modified rosin resin (YH-100C), 10 parts of isocyanate (MS-C), 0.1 parts of light stabilizer (JF-90), antioxidant (RIANOX1010)0.1 part.
实施例3Example 3
(1)将第一聚酯多元醇、第二聚酯多元醇、无定型聚酯多元醇、液态聚酯多元醇、改性松香树脂、光稳定剂和抗氧剂混合后在温度为140℃的条件下进行热熔处理，在真空度为-0.095MPa、搅拌转速为150rpm的条件下进行脱水处理，脱水时间为2h，得到处理液；(1) Mix the first polyester polyol, the second polyester polyol, amorphous polyester polyol, liquid polyester polyol, modified rosin resin, light stabilizer and antioxidant at a temperature of 140°C Carry out hot melt treatment under the conditions of -0.095MPa vacuum degree and 150rpm stirring speed for dehydration treatment. The dehydration time is 2h to obtain the treatment liquid;
(2)在氮气的保护下，将异氰酸酯加入所述处理液中，在真空度为-0.095MPa、温度为120℃、搅拌转速为150rpm的条件下进行混合反应，直至产物中异氰酸酯的质量百分含量达到2.2％，停止反应；(2) Under the protection of nitrogen, add isocyanate to the treatment liquid, and perform a mixing reaction under the conditions of a vacuum of -0.095MPa, a temperature of 120°C, and a stirring speed of 150rpm, until the mass percentage of isocyanate in the product is When the content reaches 2.2%, the reaction stops;
各原料的用量按照重量份计为：第一聚酯多元醇型号(XCP-2000PM)The dosage of each raw material is calculated in parts by weight: the first polyester polyol model (XCP-2000PM)
90份，第二聚酯多元醇(型号XCP-3000H)5份，无定型聚酯多元醇(Dynacoll-7130)4.3份，液态聚酯多元醇(Dynacoll-7250)4.3份，改性松香树脂(YH-100C)10份，异氰酸酯(MS-C)25份，光稳定剂(JF-90)0.5份，抗氧剂(RIANOX 1010)0.5份；90 parts, 5 parts of the second polyester polyol (model XCP-3000H), 4.3 parts of amorphous polyester polyol (Dynacoll-7130), 4.3 parts of liquid polyester polyol (Dynacoll-7250), modified rosin resin ( YH-100C) 10 parts, isocyanate (MS-C) 25 parts, light stabilizer (JF-90) 0.5 parts, antioxidant (RIANOX 1010) 0.5 parts;
其中，第一聚酯多元醇结构式中R1为苯酐基，R2为羟基，m＝5，n＝3，a＝7，型号XCP-2000PM(羟值53-59mgKOH/g)，分子量约为2000；第二聚酯多元醇结构式中R1为苯酐基，R2为羟基，m＝2，n＝2，a＝14，型号为XCP-3000H(羟值34-40mgKOH/g)，分子量约为3000。Among them, in the first polyester polyol structural formula, R 1 is a phthalic anhydride group, R 2 is a hydroxyl group, m=5, n=3, a=7, model XCP-2000PM (hydroxyl value 53-59 mgKOH/g), and the molecular weight is about 2000; In the second polyester polyol structural formula, R 1 is a phthalic anhydride group, R 2 is a hydroxyl group, m=2, n=2, a=14, the model is XCP-3000H (hydroxyl value 34-40mgKOH/g), the molecular weight is about for 3000.
实施例4Example 4
按照实施例1的方法制备湿固化聚氨酯热熔胶，不同的是，各原料的用量按照重量份计为：第一聚酯多元醇(型号XCP-PA110N)70份，第二聚酯多元醇(型号XCPA-195)，无定型聚酯多元醇(Dynacoll-7130)10份，液态聚酯多元醇(Dynacoll-7250)10份，改性松香树脂(YH-100C)6份，异氰酸酯(MS-C)13.5份，光稳定剂(JF-90)0.25份，抗氧剂(RIANOX 1010)0.25份；Moisture curing polyurethane hot melt adhesive was prepared according to the method of Example 1, except that the amount of each raw material was calculated in parts by weight: 70 parts of the first polyester polyol (model XCP-PA110N), 70 parts of the second polyester polyol (Model XCP-PA110N), Model ) 13.5 parts, light stabilizer (JF-90) 0.25 parts, antioxidant (RIANOX 1010) 0.25 parts;
其中，第一聚酯多元醇结构式中R1为苯酐基，R2为羟基，m＝8，n＝4，a＝3,型号XCP-PA110N(羟值104-110mgKOH/g)，分子量约为1000；第二聚酯多元醇结构式中R1为苯酐基，R2为羟基，m＝5，n＝4，a＝2，型号为XCPA-195(羟值190-205mgKOH/g)，分子量约为560。Among them, in the first polyester polyol structural formula, R 1 is a phthalic anhydride group, R 2 is a hydroxyl group, m=8, n=4, a=3, model XCP-PA110N (hydroxyl value 104-110 mgKOH/g), and the molecular weight is about 1000; in the second polyester polyol structural formula, R 1 is a phthalic anhydride group, R 2 is a hydroxyl group, m=5, n=4, a=2, the model is XCPA-195 (hydroxyl value 190-205mgKOH/g), the molecular weight is about to 560.
实施例5Example 5
按照实施例1的方法制备湿固化聚氨酯热熔胶，不同的是，各原料的用量按照重量份计为：第一聚酯多元醇(XCP-2000IPS)40份，第二聚酯多元醇(XCP-3000N)40份，无定型聚酯多元醇(Dynacoll-7130)20份，液态聚酯多元醇(Dynacoll-7250)20份，改性松香树脂(YH-100C)6份，异氰酸酯(MS-C)13.5份，光稳定剂(JF-90)0.25份，抗氧剂(RIANOX 1010)0.25份。Moisture curing polyurethane hot melt adhesive was prepared according to the method of Example 1, except that the amount of each raw material was calculated in parts by weight: 40 parts of the first polyester polyol (XCP-2000IPS), 40 parts of the second polyester polyol (XCP -3000N) 40 parts, amorphous polyester polyol (Dynacoll-7130) 20 parts, liquid polyester polyol (Dynacoll-7250) 20 parts, modified rosin resin (YH-100C) 6 parts, isocyanate (MS-C ) 13.5 parts, light stabilizer (JF-90) 0.25 parts, antioxidant (RIANOX 1010) 0.25 parts.
实施例6Example 6
按照实施例1的方法制备湿固化聚氨酯热熔胶，不同的是，各原料的用量按照重量份计为：第一聚酯多元醇(XCP-2000IPS)70份，第二聚酯多元醇(XCP-3000N)10份，改性松香树脂(YH-100C)6份，异氰酸酯(MS-C)13.5份，光稳定剂(JF-90)0.25份，抗氧剂(RIANOX1010)0.25份。Moisture curing polyurethane hot melt adhesive was prepared according to the method of Example 1, except that the amount of each raw material was calculated in parts by weight: 70 parts of the first polyester polyol (XCP-2000IPS), 70 parts of the second polyester polyol (XCP -3000N) 10 parts, modified rosin resin (YH-100C) 6 parts, isocyanate (MS-C) 13.5 parts, light stabilizer (JF-90) 0.25 parts, antioxidant (RIANOX1010) 0.25 parts.
对比例1Comparative example 1
(1)将结晶型聚酯多元醇、改性松香树脂、光稳定剂和抗氧剂混合后在温度为145℃的条件下进行热熔处理，在真空度为-0.098MPa、搅拌转速为175rpm的条件下进行脱水处理，脱水时间为1.5h，得到处理液；(1) Mix crystalline polyester polyol, modified rosin resin, light stabilizer and antioxidant and perform hot melt treatment at a temperature of 145°C. The vacuum degree is -0.098MPa and the stirring speed is 175rpm. Carry out dehydration treatment under the conditions, the dehydration time is 1.5h, and the treatment liquid is obtained;
(2)在氮气的保护下，将异氰酸酯加入所述处理液中，在真空度为-0.098MPa、温度为100℃、搅拌转速为175rpm的条件下进行混合反应，直至产物中异氰酸酯的质量百分含量达到2.0％，停止反应；(2) Under the protection of nitrogen, add isocyanate into the treatment liquid, and carry out a mixing reaction under the conditions of a vacuum of -0.098MPa, a temperature of 100°C, and a stirring speed of 175rpm, until the mass percentage of isocyanate in the product is When the content reaches 2.0%, the reaction stops;
各原料的用量按照重量份计为：结晶型聚酯多元醇(XCP-44)20份，结晶型聚酯多元醇(XCP-3000B)20份，改性松香树脂(YH-100C)6份，异氰酸酯(MS-C)13.5份，光稳定剂(JF-90)0.25份，抗氧剂(RIANOX 1010)0.25份。The dosage of each raw material is calculated 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 parts of light stabilizer (JF-90), 0.25 parts of antioxidant (RIANOX 1010).
对比例2Comparative example 2
将第一聚酯多元醇、第二聚酯多元醇、无定型聚酯多元醇、液态聚酯多元醇、异氰酸酯、改性松香树脂、光稳定剂和抗氧剂混合后在温度为145℃的条件下进行热熔处理，在真空度为-0.098MPa、搅拌频率为75Hz的条件下进行脱水处理，直至产物中异氰酸酯的质量百分含量达到2.0％，停止反应；The first polyester polyol, the second polyester polyol, amorphous polyester polyol, liquid polyester polyol, isocyanate, modified rosin resin, light stabilizer and antioxidant are mixed at a temperature of 145°C. Carry out hot melt treatment under the conditions, and perform dehydration treatment under the conditions of vacuum degree of -0.098MPa and stirring frequency of 75Hz until the mass percentage of isocyanate in the product reaches 2.0% and stop the reaction;
各原料的用量按照重量份计为：第一聚酯多元醇(XCP-2000IPS)70份，第二聚酯多元醇(XCP-3000N)10份，无定型聚酯多元醇(Dynacoll-7130)10份，液态聚酯多元醇(Dynacoll-7250)10份，改性松香树脂(YH-100C)6份，异氰酸酯(MS-C)13.5份，光稳定剂(JF-90)0.25份，抗氧剂(RIANOX1010)0.25份。The amount of each raw material used is calculated in parts by weight: 70 parts of the first polyester polyol (XCP-2000IPS), 10 parts of the second polyester polyol (XCP-3000N), 10 parts of the amorphous polyester polyol (Dynacoll-7130) parts, 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 parts of light stabilizer (JF-90), antioxidant (RIANOX1010) 0.25 parts.
对比例3Comparative example 3
某市售湿固化聚氨酯热熔胶(XCUR-6018)。A commercially available moisture-curing polyurethane hot melt adhesive (XCUR-6018).
测试例test case
将实施例1-实施例6制备得到的湿固化聚氨酯热熔胶和对比例1-对比例3进行粘度、开放时间、初始剥离强度和最终剥离强度测试，结果见表1。The moisture-curing polyurethane hot melt adhesive prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were tested for viscosity, open time, initial peel strength and final peel strength. The results are shown in Table 1.
将实施例1-实施例6制备得到的湿固化聚氨酯热熔胶和对比例1-对比例3进行PVC膜/木塑板粘接性能测试，结果见表2。The moisture-curing polyurethane hot melt adhesive prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to PVC film/wood-plastic board bonding performance testing. The results are shown in Table 2.
表1Table 1
表2Table 2
通过表1和表2的结果可以看出，实施例1-实施例6采用本发明提供的制备方法得到的湿固化聚氨酯热熔胶相较于对比例1-对比例3表现出更好的初始剥离强度和较高的最终剥离强度，粘接效果明显提升。It can be seen from the results in Table 1 and Table 2 that the moisture-curing polyurethane hot melt adhesives obtained in Examples 1 to 6 using the preparation method provided by the present invention show better initial properties than Comparative Examples 1 to 3. Peel strength and higher final peel strength, the bonding effect is significantly improved.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。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 concept of the present invention, many simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
Claims (5)
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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 |
| 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 |
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| 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 |
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