CN115926727A - Solvent-free bi-component polyurethane adhesive for paper-plastic compounding - Google Patents
Solvent-free bi-component polyurethane adhesive for paper-plastic compounding Download PDFInfo
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- CN115926727A CN115926727A CN202211572529.1A CN202211572529A CN115926727A CN 115926727 A CN115926727 A CN 115926727A CN 202211572529 A CN202211572529 A CN 202211572529A CN 115926727 A CN115926727 A CN 115926727A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 61
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 61
- 229920003023 plastic Polymers 0.000 title claims abstract description 51
- 239000004033 plastic Substances 0.000 title claims abstract description 51
- 238000013329 compounding Methods 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 239000003292 glue Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- 230000032050 esterification Effects 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 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 15
- 239000002253 acid Substances 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- -1 3, 5-di-t-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000005086 pumping Methods 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000012466 permeate Substances 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 4
- 239000005025 cast polypropylene Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000011091 composite packaging material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920013710 Dow VORANOL™ CP 450 Polyol Polymers 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012205 single-component adhesive Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a solvent-free bi-component polyurethane adhesive for paper-plastic compounding, which comprises an adhesive A and an adhesive B. And (2) mixing the polyester polyol and the polyether polyol in parts by mass of 25-40 and 5-15, vacuum dehydrating, and performing crosslinking reaction on the mixture at the temperature of 80-90 ℃ and 55-65 parts by mass of isocyanate until the NCO% is 12-16% to obtain the A adhesive. At N 2 Under protection, the dicarboxylic acid, the diol and the antioxidant are mixed in parts by mass of 50 to 65, 35 to 50 and 0.006 to 0.01, and the mixture is subjected to esterification and dehydration at 150 to 180 ℃ for 4 +/-0.5 h; heating to 190-210 ℃, and keeping the temperature for 3 +/-0.5 h; heating to 220-230 ℃ for reaction, adding a catalyst, and carrying out vacuum polycondensation to obtain the B glue. Application of the inventionThe solvent-free bi-component polyurethane adhesive for paper-plastic compounding is not easy to permeate into paper, has high bonding strength and good appearance transparency after bonding.
Description
Technical Field
The invention belongs to the technical field of paper-plastic composite packaging materials, and particularly relates to a solvent-free bi-component polyurethane adhesive for paper-plastic composite.
Background
With the improvement of environmental awareness and the stricter environmental requirements, the reduction of the discharge amount of VOCs and carbon has become a future trend, and the environment-friendly and efficient solvent-free composite process is applied to more and more enterprises. The paper-plastic composite packaging material is a composite material which takes paper as a main base material and is bonded with other base materials through a composite process to have certain functionality, has the characteristics of good appearance, high strength, good waterproofness and the like, is one of the most widely applied packaging materials at present, and is generally applied to the industries of food, daily chemicals, sanitary products and the like.
In the paper-plastic composite process, the solvent-free single-component polyurethane adhesive is not easily absorbed by paper excessively to cause the existing adhesive shortage, has good bonding effect and is more suitable for being applied to the paper-plastic composite process, but the curing mode is moisture curing, so that the appearance transparency is poor after curing, and the application of the adhesive is limited in the field with strict requirements on the appearance of paper-plastic composite packaging. For example, chinese patent CN106854449B discloses a solvent-free single component glue for paper-plastic compounding and a preparation method thereof, wherein the viscosity of the prepared solvent-free single component glue is relatively high, the lowest viscosity at 30 ℃ also reaches 190000mpa.s, the viscosity is too high, so that the leveling property of the glue is poor, the peel strength after single component curing is relatively low, and the bonding effect is poor. In addition, because the single-component glue is cured by moisture, the windowing part of the package is fuzzy and opaque after curing, and the appearance is influenced.
Disclosure of Invention
The purpose of the invention is as follows: the solvent-free bi-component polyurethane adhesive for paper-plastic compounding is provided, the adhesive is not easy to permeate into paper, the bonding strength is high, and the appearance transparency after bonding is good.
The technical scheme of the invention is as follows:
a solvent-free bi-component polyurethane adhesive for paper-plastic compounding comprises an adhesive A and an adhesive B, wherein the preparation method of the adhesive A comprises the following steps: uniformly mixing 25-40 parts by mass of polyester polyol and 5-15 parts by mass of polyether polyol, and dehydrating at 110-120 ℃ under a vacuum condition until the water content is lower than 200ppm; then, the mixture is crosslinked and reacted with 55 to 65 mass portions of isocyanate for 3 to 5 hours at the temperature of between 80 and 90 ℃ until the NCO percent of the system is between 12 and 16 percent to obtain A glue;
the preparation method of the adhesive B comprises the following steps:
at N 2 Under protection, adding 50-65 parts by mass of dicarboxylic acid, 35-50 parts by mass of dihydric alcohol and 0.006-0.01 part by mass of antioxidant into a reaction kettle, stirring, heating to 150-180 ℃, and keeping the temperature for 4 +/-0.5 h to perform esterification dehydration; continuously heating to 190-210 ℃, and keeping the temperature for 3 +/-0.5 h; continuously slowly heating to 220-230 ℃, carrying out heat preservation reaction until the acid value is less than 5mg.KOH/g, adding 0.006-0.01 part by mass of catalyst for vacuum polycondensation until the acid value of the system is less than 2mg.KOH/g and the hydroxyl value is 80-100mg.KOH/g, and obtaining B glue;
wherein the molecular weight of the polyester polyol is 900-1000, and the functionality is 2-3; the molecular weight of the polyether polyol is 400-2000, and the functionality is not lower than 3; the dicarboxylic acid is at least one of terephthalic acid, phthalic anhydride, isophthalic acid and adipic acid; the dihydric alcohol is at least one of diethylene glycol, ethylene glycol, neopentyl glycol, methyl propylene glycol and butanediol.
The invention is used in the solvent-free bi-component polyurethane adhesive for paper-plastic compounding:
1. the polyester polyol selected for the glue A not only contains ester groups with larger polarity, but also contains aliphatic chain segments with softer chain segments.
2. The ester bond has high polarity and high cohesive strength; meanwhile, the selected polyester polyol has higher functionality, can provide main bonding force of the adhesive A and improve initial bonding force.
3. The softer fatty chain segment can ensure that the molecular chain segment has good fluidity on the premise of keeping the A glue with great adhesive force, so that the A glue has high adhesive strength and low viscosity.
The polyether polyol selected from the A glue has flexibility, can reduce the viscosity of a system, has high functionality, is mixed with the polyester polyol in a proper proportion, can effectively adjust the cohesive strength of the glue, and is a key factor for good transfer in a compounding process. The adhesive B is prepared from proper polyalcohol and dibasic acid, so that good initial adhesion is guaranteed, high adhesion strength is provided, and low viscosity is achieved.
Preferably, the polyester polyol is a castor oil polyol.
Preferably, the isocyanate is at least one of isophorone diisocyanate, diphenylmethane diisocyanate, a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, and hexamethylene diisocyanate.
Preferably, the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Preferably, the catalyst is at least one of dibutyltin dilaurate, stannous octoate, tetrabutyl titanate, tetraisopropyl titanate, and dibutyltin.
Preferably, in the preparation method of the A glue, intermittent vacuum pumping and defoaming are carried out in the crosslinking reaction.
Preferably, the mass ratio of the glue A to the glue B is 100.
The invention has the beneficial effects that:
the solvent-free bi-component polyurethane adhesive for the paper-plastic composite material has the following advantages
1. The initial adhesion is large, and the phenomena of paper glue permeation and color change are not easy to occur in the paper-plastic compounding process;
2. the peel strength of the cured paper-plastic composite material is high;
the leveling property of the glue A and the glue B is good, and high-speed coating operation is facilitated;
4. vacuum defoaming is carried out under proper reaction conditions, which is beneficial to the polymerization reaction, increases the viscosity of the system and prevents glue leakage;
5. the two components are mainly crosslinked and cured, so that the appearance transparency is better, and the paper-plastic visual package has high appearance transparency and is superior to single-component glue compounding.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The preparation method of the solvent-free bi-component polyurethane adhesive for paper-plastic compounding comprises the following steps:
step one, preparing glue A:
respectively taking 31.7 parts by mass of castor oil polyol with average functionality of 2.7 and molecular weight of 900-1000; 6.5 parts by mass of polyether polyol VORANOL CP450 with the molecular weight of 450 and the functionality of 3 are uniformly mixed, vacuum dehydration is carried out at 120 ℃ until the water content of the system is lower than 200ppm, 6 parts by mass of diphenylmethane diisocyanate and 56 parts by mass of a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate are added, the temperature is controlled to be 80-90 ℃ for crosslinking reaction, intermittent vacuum pumping and defoaming are carried out during the crosslinking reaction, the reaction is stopped when the NCO (namely the percentage content of isocyanate groups) value of the system is determined to be 15.8 percent, and the A adhesive is obtained.
Step two, preparing glue B:
N 2 under protection, 39.8 parts by mass of diethylene glycol, 5.0 parts by mass of ethylene glycol, 28.2 parts by mass of isophthalic acid, 27 parts by mass of adipic acid, and tris [ 2.4-di-tert-butylphenyl ]]Adding 0.008 mass part of phosphite ester into a reaction kettle, stirring and heating to 150-180 ℃, preserving heat for 4 hours, and esterifying and dehydrating the system; continuously heating to 190-210 ℃, and preserving heat for 3h; and continuously slowly heating to 220-230 ℃, preserving the temperature, reacting until the acid value is 4.0mg.KOH/g, adding 0.008 mass part of catalyst tetrabutyl titanate, and carrying out vacuum polycondensation until the acid value and the hydroxyl value of the system are 0.56mg.KOH/g and 80mg.KOH/g respectively to obtain the B glue.
Thirdly, preparing a solvent-free two-component polyurethane adhesive for paper-plastic compounding:
mixing the glue A and the glue B according to a mass ratio of 100 to 80 to obtain the solvent-free two-component polyurethane adhesive for paper-plastic compounding.
Example 2
Step one, preparing glue A:
respectively taking 38.8 parts by mass of modified castor oil polyol with average functionality of 2.5 and molecular weight of 900-1000; 5.5 parts by mass of polyether polyol (model number is Donol DJ 12K) with molecular weight of 1000 and functionality of 4 are uniformly mixed, vacuum dehydration is carried out at 110 ℃ until the water content of the system is lower than 200ppm, 43.3 parts by mass of the mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate and 12.4 parts by mass of isophorone diisocyanate are added, the temperature is controlled at 80-90 ℃ for crosslinking reaction, intermittent vacuum-pumping defoaming is carried out during the crosslinking reaction for 5 hours, and the reaction is stopped when the NCO% value of the system is measured to be 13.5%, so that the A adhesive is obtained.
Step two, preparing glue B:
under the protection of N2, adding 25 parts by mass of methyl propylene glycol, 13.5 parts by mass of ethylene glycol, 33.5 parts by mass of isophthalic acid, 28 parts by mass of adipic acid and 0.006 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester into a reaction kettle, stirring and heating to 150-180 ℃, preserving heat for 3.5 hours, and esterifying and dehydrating the system; continuously heating to 190-210 ℃, and preserving heat for 3.5h; and (3) continuously and slowly heating to 220-230 ℃, preserving the temperature, reacting until the acid value is 3.8mg.KOH/g, adding 0.006 mass part of dibutyltin dilaurate serving as a catalyst, and carrying out vacuum polycondensation until the acid value of the system is 0.45mg.KOH/g and the hydroxyl value is 90mg.KOH/g to obtain the B glue.
Thirdly, preparing the paper-plastic composite solvent-free two-component polyurethane adhesive:
and mixing the glue A and the glue B according to the mass ratio of 1.
Example 3
Step one, preparing glue A:
respectively taking 25.3 parts by mass of modified castor oil polyhydric alcohol with functionality of 3 and molecular weight of 900-1000; 15 parts of polyether polyol (VOANOL 3010 and VOANOL CP-1055 in a molar ratio of 1: 1) with the molecular weight of 2000 and the functionality of 3 are uniformly mixed, vacuum dehydration is carried out at 115 ℃ until the water content of the system is lower than 200ppm, 4.2 parts of hexamethylene diisocyanate and 55.5 parts of mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate are added, the temperature is controlled at 80-90 ℃ for crosslinking reaction for 4 hours, vacuum degassing is intermittently carried out during the crosslinking reaction, and the reaction is stopped when the NCO% value of the system is measured to be 16%, so that the A adhesive is obtained.
Step two, preparing glue B:
N 2 adding 35 parts by mass of ethylene glycol, 33 parts by mass of phthalic anhydride, 32 parts by mass of adipic acid and 0.01 part by mass of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate into a reaction kettle under protection, stirring and heating to 150-180 ℃, preserving heat for 4.5 hours, and esterifying and dehydrating the system; continuously heating to 190-210 ℃, and preserving heat for 2.5h; and continuously slowly heating to 220-230 ℃, preserving the temperature, reacting until the acid value is 4.1mg.KOH/g, adding 0.008 mass part of catalyst stannous octoate, and carrying out vacuum polycondensation until the acid value of the system is 1.0mg.KOH/g and the hydroxyl value is 100mg.KOH/g to obtain the B glue.
Step three, preparing a solvent-free two-component polyurethane adhesive for paper-plastic compounding:
mixing the glue A and the glue B according to a mass ratio of 100 to obtain the solvent-free two-component polyurethane adhesive for paper-plastic compounding.
Example 4
Step one, preparing glue A:
respectively taking 32 parts by mass of castor oil polyol with the functionality of 2.7 and the molecular weight of 900-1000; 10.5 parts by mass of polyether polyol VOANOL CP-1055 with the molecular weight of 1000 and the functionality of 3.0, uniformly mixing, carrying out vacuum dehydration at 120 ℃ until the water content of the system is lower than 200ppm, adding 57.5 parts by mass of a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, carrying out crosslinking reaction for 4 hours at the temperature of 80-90 ℃, intermittently vacuumizing and defoaming during the crosslinking reaction, and stopping the reaction when the NCO% value of the system is determined to be 12.5% to obtain the A glue.
Step two, preparing glue B:
N 2 adding 42 mass portions of butanediol, 36 mass portions of terephthalic acid, 22 mass portions of adipic acid and 0.01 mass portion of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate into a reaction kettle under protection, stirring and heating to 150-180 DEG CKeeping the temperature for 3.5h, and esterifying and dehydrating the system; continuously heating to 190-210 ℃, and preserving heat for 3.5h; and continuously slowly heating to 220-230 ℃, preserving heat, reacting until the acid value is 3.7mg.KOH/g, adding 0.008 mass part of catalyst stannous octoate, and carrying out vacuum polycondensation until the acid value of the system is 0.8mg.KOH/g and the hydroxyl value is 100mg.KOH/g to obtain the B glue.
Step three, preparing a solvent-free two-component polyurethane adhesive for paper-plastic compounding:
mixing the glue A and the glue B according to a mass ratio of 100 to obtain the solvent-free two-component polyurethane adhesive for paper-plastic compounding.
Example 5
Step one, preparing glue A:
respectively and uniformly mixing 34.2 parts by mass of modified castor oil polyol with the functionality of 2.7, the molecular weight of 900-1000, 5.2 parts by mass of polyether polyol VOANOL 2070 with the molecular weight of 700 and the functionality of 3, then dehydrating in vacuum at 120 ℃ until the water content of the system is lower than 200ppm, adding 5.6 parts by mass of isophorone diisocyanate and 55 parts by mass of a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, carrying out crosslinking reaction for 4 hours at the temperature of 80-90 ℃, intermittently vacuumizing and defoaming during the process, and stopping the reaction when the NCO% value of the system is determined to be 15.5% to obtain the A adhesive.
Step two, preparing glue B:
N 2 under protection, 43.3 parts by mass of neopentyl glycol, 4.8 parts by mass of ethylene glycol, 30.8 parts by mass of phthalic anhydride, 21.1 parts by mass of adipic acid and 0.01 part by mass of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate are added into a reaction kettle, stirred and heated to 150-180 ℃, the temperature is kept for 4 hours, and the system is esterified and dehydrated; continuously heating to 190-210 ℃, and preserving heat for 2.5h; and continuously slowly heating to 220-230 ℃, preserving the temperature, reacting until the acid value is 3.5mg.KOH/g, adding 0.01 mass part of dibutyltin catalyst into the mixture, and carrying out vacuum polycondensation until the acid value of the system is 0.74mg.KOH/g and the hydroxyl value is 100mg.KOH/g, thus obtaining the adhesive B.
Step three, preparing a solvent-free two-component polyurethane adhesive for paper-plastic compounding:
mixing the glue A and the glue B according to a mass ratio of 100 to obtain the solvent-free two-component polyurethane adhesive for paper-plastic compounding.
Comparative example 1
The preparation method of the solvent-free single-component glue for paper-plastic compounding comprises the following components: 40kg of pure diphenylmethane-4, 4' -diisocyanate (MDI); 10kg of liquefied MDI; 5kg of polyoxypropylene glycol; 45kg of polyethylene glycol adipate; 0.005kg of phosphoric acid. Wherein, the molecular weight of the polyoxypropylene diol is 400-2000, and the molecular weight of the polyethylene glycol adipate is 500-2000. The preparation method of the solvent-free single-component adhesive for paper-plastic compounding comprises the following steps: step 1: adding pure MDI, liquefied MDI, polyoxypropylene glycol and phosphoric acid into a reaction kettle for reaction, wherein the reaction time is 60 minutes, and the reaction temperature is 76-80 ℃; and 2, step: after the reaction in the step 1 is finished, adding polyethylene glycol adipate into the reaction kettle in the step 1 for reaction, wherein the reaction time is 30 minutes, and the reaction temperature is 76-80 ℃; and 3, step 3: and (3) after the reaction in the step (2) is finished, vacuumizing and defoaming for 60 minutes at the reaction temperature of 76-80 ℃ and the vacuum degree of 0.09MPa to obtain the solvent-free single-component glue for paper-plastic compounding.
Performance testing
1. Viscosity measurement
The viscosities of the adhesives for paper-plastic composites prepared in the examples and comparative examples were measured according to the method of "determination of adhesive viscosity" GB/T2794-1995, and the results are shown in Table 1:
TABLE 1
2. Determination of the Properties of paper-Plastic composite products
The viscosity of the solvent-free bi-component adhesive for paper-plastic compounding prepared in each example was subjected to paper-plastic compounding, and then performance measurement was performed.
Paper-plastic compounding: the thickness of kraft paper for paper-plastic compounding is 70-80 μm, the cast polypropylene CPP and biaxially oriented polypropylene BOPP are respectively selected for plastics on two sides, namely, the extinction BOPP/kraft paper/CPP is compounded, and the window opening part is the extinction BOPP/PET/CPP. Solvent-free composite time adhesiveThe cylinder temperature is set at 65 ℃, and the composite roll temperature is set at 65 ℃; the glue applying amount is 3-4g/m 2 (ii) a Curing temperature is 50-55 ℃; the curing time is 36h.
And (3) testing the glue permeability: if glue permeates into the paper in the compounded or cured sample, the color of the paper becomes dark and discolored, the glue permeation degree is determined according to the dark degree, and the test result is shown in table 2.
Leveling property of glue: and (3) observing whether the paper-plastic composite sample is white spots, bubbles and the like in the appearance, and if the leveling property is not proved to be good, the test result is shown in table 2.
Transparency after paper-plastic compounding: the cured paper-plastic composite sample is observed to see whether the appearance of the windowed part is transparent or not, and the test result is shown in table 2.
And (3) testing the peel strength: cutting the sample into a sample strip with the width of 15.0 +/-0.1 mm and the length of 200 mm; peeling the composite layer and the base material by 50mm in advance along the length direction of the sample, stretching 100mm on an intelligent electronic tensile testing machine XLW-500N at the speed of 300 +/-50 mm/min for T-shaped peeling, observing the fiber damage degree of the paper after the completion, wherein the larger the damage area is, the better the peeling effect is, and the percentage area of the paper fiber damage is used for representing the peeling strength; the test results are shown in Table 2.
TABLE 2
| Examples of the invention | Adhesive bleeding Property | Leveling property | Transparency of | Area of paper fiber failure (%) |
| Example 1 | Non-permeable adhesive | Good leveling property | Is transparent | 100 |
| Example 2 | Non-permeable adhesive | Good leveling property | Is transparent | 100 |
| Example 3 | Non-permeable adhesive | Good leveling property | Is transparent | 100 |
| Example 4 | Non-permeable adhesive | Good leveling property | Is transparent | 100 |
| Example 5 | Non-permeable adhesive | Good leveling property | Is transparent | 100 |
| Comparative example 1 | Partially penetrated glue | Poor leveling property | Blurred opacity | 80 |
As can be seen by comparing the tables 1 and 2, compared with the single component, the solvent-free bi-component adhesive for compounding the paper and the plastic produced by the invention has great advantage in viscosity, not only ensures that the glue has certain leveling property, but also is not easy to cause glue seepage phenomenon, and ensures that the paper and the plastic have stronger peel strength. In addition, the solvent-free bi-component polyurethane adhesive for paper-plastic compounding is bi-component, compared with the single component, the appearance transparency has great advantage, the single component is cured by moisture, the windowing part is fuzzy and opaque after curing, and the bi-component is cross-linking reaction between the A and B bi-components, so the transparency is relatively higher.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features related to the embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive labor based on the embodiments in the present invention are within the protection scope of the present invention.
Claims (7)
1. A solvent-free bi-component polyurethane adhesive for paper-plastic compounding comprises an adhesive A and an adhesive B, and is characterized in that the preparation method of the adhesive A is as follows:
uniformly mixing 25-40 parts by mass of polyester polyol and 5-15 parts by mass of polyether polyol, and dehydrating at 110-120 ℃ under a vacuum condition until the water content is lower than 200ppm; then, carrying out crosslinking reaction with 55-65 parts by mass of isocyanate at 80-90 ℃ for 3-5 hours until the NCO% of the system is 12-16% to obtain A glue;
the preparation method of the adhesive B comprises the following steps:
at N 2 Under protection, adding 50-65 parts by mass of dicarboxylic acid, 35-50 parts by mass of dihydric alcohol and 0.006-0.01 part by mass of antioxidant into a reaction kettle, stirring, heating to 150-180 ℃, and keeping the temperature for 4 +/-0.5 h to perform esterification and dehydration; continue to useHeating to 190-210 ℃, and keeping the temperature for 3 +/-0.5 h; continuously slowly heating to 220-230 ℃, carrying out heat preservation reaction until the acid value is less than 5mg.KOH/g, adding 0.006-0.01 part by mass of catalyst for vacuum polycondensation until the acid value of the system is less than 2mg.KOH/g and the hydroxyl value is 80-100mg.KOH/g, and obtaining B glue;
wherein the molecular weight of the polyester polyol is 900-1000, and the functionality is 2-3; the molecular weight of the polyether polyol is 400-2000, and the functionality is not lower than 3; the dicarboxylic acid is at least one of terephthalic acid, phthalic anhydride, isophthalic acid and adipic acid; the dihydric alcohol is at least one of diethylene glycol, ethylene glycol, neopentyl glycol, methyl propylene glycol and butanediol.
2. The solvent-free two-component polyurethane adhesive for paper-plastic composite as claimed in claim 1, wherein the polyester polyol is castor oil polyol.
3. The solvent-free two-component polyurethane adhesive for paper-plastic compounding of claim 1, wherein the isocyanate is at least one of isophorone diisocyanate, diphenylmethane diisocyanate, a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, and hexamethylene diisocyanate.
4. The solvent-free two-component polyurethane adhesive for paper-plastic composite as claimed in claim 1, wherein the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-t-butylphenyl ] phosphite and n-octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate.
5. A solventless, two component polyurethane adhesive for paper-plastic composites as claimed in claim 1 wherein the catalyst is at least one of dibutyltin dilaurate, stannous octoate, tetrabutyl titanate and dibutyltin.
6. The solvent-free two-component polyurethane adhesive for paper-plastic composite as claimed in claim 1, wherein the preparation method of the A glue is characterized in that the crosslinking reaction is carried out with intermittent vacuum-pumping and defoaming.
7. A solvent-free two-component polyurethane adhesive for paper-plastic composite as claimed in any one of claims 1 to 6, wherein the mass ratio of the glue A to the glue B is 100.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423741A (en) * | 2008-11-10 | 2009-05-06 | 于龙洲 | Polyurethane adhesive for plastic-paper composite and preparation method thereof |
| CN103820069A (en) * | 2014-03-18 | 2014-05-28 | 新东方油墨有限公司 | Double-component solvent-free polyurethane adhesive and preparation method thereof |
| CN107722917A (en) * | 2017-10-31 | 2018-02-23 | 江苏力合粘合剂有限公司 | A kind of preparation method of solvent-free dual-component polyurethane boiling adhesive |
| EP3327056A1 (en) * | 2016-11-25 | 2018-05-30 | Henkel AG & Co. KGaA | Low viscosity, fast curing adhesive laminate-composition |
| CN109476974A (en) * | 2016-07-12 | 2019-03-15 | 博斯蒂克股份公司 | Adhesive two-component composition based on polyurethane |
| CN109642142A (en) * | 2016-07-12 | 2019-04-16 | 博斯蒂克股份公司 | Adhesive two-component composition based on polyurethane |
| WO2022172760A1 (en) * | 2021-02-09 | 2022-08-18 | Dic株式会社 | Adhesive, laminate, and packaging material |
-
2022
- 2022-12-08 CN CN202211572529.1A patent/CN115926727A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423741A (en) * | 2008-11-10 | 2009-05-06 | 于龙洲 | Polyurethane adhesive for plastic-paper composite and preparation method thereof |
| CN103820069A (en) * | 2014-03-18 | 2014-05-28 | 新东方油墨有限公司 | Double-component solvent-free polyurethane adhesive and preparation method thereof |
| CN109476974A (en) * | 2016-07-12 | 2019-03-15 | 博斯蒂克股份公司 | Adhesive two-component composition based on polyurethane |
| CN109642142A (en) * | 2016-07-12 | 2019-04-16 | 博斯蒂克股份公司 | Adhesive two-component composition based on polyurethane |
| EP3327056A1 (en) * | 2016-11-25 | 2018-05-30 | Henkel AG & Co. KGaA | Low viscosity, fast curing adhesive laminate-composition |
| CN107722917A (en) * | 2017-10-31 | 2018-02-23 | 江苏力合粘合剂有限公司 | A kind of preparation method of solvent-free dual-component polyurethane boiling adhesive |
| WO2022172760A1 (en) * | 2021-02-09 | 2022-08-18 | Dic株式会社 | Adhesive, laminate, and packaging material |
Non-Patent Citations (1)
| Title |
|---|
| 汪阳: "软包装用无溶剂类双组份聚氨酯胶粘剂的合成研究", 国优秀硕士学位论文全文数据库工程科技Ⅰ辑, no. 2, 15 February 2015 (2015-02-15), pages 016 - 427 * |
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