CN1740259A - Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process - Google Patents
Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process Download PDFInfo
- Publication number
- CN1740259A CN1740259A CN 200510104822 CN200510104822A CN1740259A CN 1740259 A CN1740259 A CN 1740259A CN 200510104822 CN200510104822 CN 200510104822 CN 200510104822 A CN200510104822 A CN 200510104822A CN 1740259 A CN1740259 A CN 1740259A
- Authority
- CN
- China
- Prior art keywords
- mixture
- tackiness agent
- acid
- glycol
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 15
- 239000000853 adhesive Substances 0.000 title claims abstract description 13
- 239000004814 polyurethane Substances 0.000 title abstract description 12
- 229920002635 polyurethane Polymers 0.000 title abstract description 12
- 239000002904 solvent Substances 0.000 title abstract description 7
- 238000010422 painting Methods 0.000 title abstract 3
- 238000000034 method Methods 0.000 title description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxytrimethylene Polymers 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-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
- 238000003756 stirring Methods 0.000 claims description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 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
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 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 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 2
- 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 2
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 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 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 claims description 2
- 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 2
- 150000001913 cyanates Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 229920005862 polyol Polymers 0.000 abstract description 5
- 150000003077 polyols Chemical class 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 235000021050 feed intake Nutrition 0.000 description 5
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The single-component no-solvent polyurethane adhesive for low temperature painting is prepared with polyester polyol, polyether polyol, polyisocyanate, catalyst, tackifier, water eliminating agent and chain expander. The adhesive is mixture of both polyester polyurethane-polyisocyanate and polyether polyurethane-polyisocyanate, and has the features of high strength, high hydrolysis resistance, no organic solvent, no use pollution and capability of painting and compounding at low temperature of 40-50 deg.c.
Description
Technical field
The invention belongs to the polymer binder technical field, more particularly, is a kind of single-component solvent-free polyurethane binder that can low temperature coated operation.
Background technology
Polyurethane adhesive is subjected to common concern, because it has good bonding, good solubility-resistence, oil-proofness and water resisting property to extensive substrate surface, even glued membrane also has very high snappiness at low temperatures simultaneously.The main machining method of making the food packing composite film material is that dry type is compound, and the tackiness agent that is adopted is to be the solvent-based adhesive of the polyurethane series of medium with the organic solvent for a long time.This class tackiness agent is because of with an organic solvent, there are contaminate environment and security problems, again owing to have not that problems such as pollution, solvent price increase in addition may take place packed article the evaporable solvent in that composite membrane is residual, need the existence of energy-conservation or the like problem, use solvent-based adhesive to be restricted.Simultaneously, two component adhesive requires accurately to measure and mix the difficulty of each component on Technology, has caused the exploitation of simpler single-component system on the technology.
At present, the advanced producer of studying the single-component solvent-free tackiness agent in the world mainly is Henkel, Novacote, Rohm﹠amp; Haas, Morton etc., their single-component solvent-free polyurethane binder is mainly concentrated and is the compound product of using of high temperature coating, coating temperature even up to 100 ℃ generally more than 80 ℃, can reduce viscosity though heat, coating easily, but temperature is too high, and adhesive reaction is fast, and it is also fast that viscosity increases, the lost of life that causes tackiness agent in the use is unfavorable for coating.Simultaneously, the viscosity of glue spread and tackiness agent just has very big relation, and glue spread was big when viscosity was high, and glue spread was little when viscosity was low.Obtain stable glue spread, will reduce the variation of adhesive viscosities as far as possible.And the coating rubber roll of solvent-free equipment complex is immersed in the tackiness agent more than 80 ℃ for a long time, is easy to cause the distortion and the damage of coating rubber roll.This recombining process and equipment to compound producer has proposed comparatively harsh requirement, and energy consumption is big simultaneously.Provide a kind of adhesive for solvent-free use that can use at a lower temperature among the patent CN 1092694C of Germany Morton company, use methacrylic ester or Lustrex or copolymer-modified urethane and get, synthesis technique is complicated, and the use temperature of its urethane adhesive for solvent-free use still is in the high temperature coating stage, be that with difference of the present invention the composition of tackiness agent is different with technology, use temperature is also different.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of single-component system that does not have a solvent is provided, can under 40～50 ℃ cold condition, be coated with the new polyurethane binder of compound.
The raw material of one-component solvent-free polyurethane mixture of the present invention and content thereof (mass fraction): polyester polyol 10-30 part, polyether glycol 50-80 part, polyisocyanates 40-65 part, catalyzer 0.005-0.03 part, tackifier 0.5-2.0 part, chainextender 0.5-4.0 part, water-removal agent 0-1.5 part.
Polyester polyol described in the present invention is by low-molecular-weight alkylol cpd and low-molecular-weight acid compound, the esterification condensation reaction takes place and macromolecular compound, molecular weight ranges at 700～1200 range of viscosities at 800-1200mPa.s.Described low mass molecule alcohol thing comprises 1,2 one propylene glycol, glycol ether, 2-methyl isophthalic acid, ammediol, a condensed ethandiol, neopentyl glycol, 1, and the 4-butyleneglycol is at the mixture of interior two or more; Described low molecular acid thing comprises two or more mixture of oxalic acid, m-phthalic acid, sebacic acid, terephthalic acid, and concrete preparation method sees CN 00103599.1.
Polyether glycol described in the present invention comprises any of polyoxypropyleneglycol, polyoxytrimethylene triol, Viscotrol C, polybutadiene diol, polytetrahydrofuran diol, and its molecular weight is that 1000-2000, viscosity are 500～1200mPa.s.
Polyisocyanates described in the present invention comprises tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI) is at interior any, two or more mixture.
Catalyzer described in the present invention mainly be catalysis-OH and-NCO between the reaction and catalysis-H
2O and-NCO between catalyst for reaction, comprise dibutyl tin laurate (DBTDL), N,N-Dibenzylamine (DMDEE), stannous octoate, triethylamine any, two or more mixture.
Chainextender described in the present invention comprises 1,4-butyleneglycol, neopentyl glycol, neopentyl glycol, to hydroxymethyl-cyclohexane at interior any, two or more mixture.
Tackifier described in the present invention are the modified high-molecular resin, comprise phenol aldehyde modified rosin TX-1, TX-2 or phenol aldehyde modified terpene phenolic resin TX-3, TX-4 any, two or more mixture, main effect is the initial bonding strength that increases tackiness agent.
It is the moisture of removing in the reaction product tackiness agent that water-removal agent described in the present invention mainly acts on, improve to store property, comprise Benzoyl chloride, vinyltrimethoxy silane, molecular sieve powder, tolylsulfonyl isocyanic ester any, two or more mixture.
The preparation method of one-component solvent-free polyurethane adhesive of the present invention, comprise following process: the pure and mild polyether glycol of polyester polyols is joined in the reactor, be heated to 50-55 ℃, add polyisocyanates again, control reaction temperature is 80-85 ℃, react and add catalyzer and chainextender after 30 minutes, continue reaction 30 minutes, add tackifier at last, continued stirring reaction 10 minutes, the mass percent that promptly obtains molecular weight and be 8000-12000, end-NCO is that 4.5-5.5%, 30 ℃ of viscosity are the adhesive product of 1500-3000mPa.s.
The single-component solvent-free tackiness agent that the present invention obtains is the polymeric polyisocyanate performed polymer that contains end NCO group, is to divide and be coated with the water that composite membrane adheres to by water in air to react and solidified with it, and its reaction expression is as follows:
The single-component solvent-free tackiness agent of the present invention preparation is by the polyether(poly)urethane polymeric polyisocyanate shown in the formula (i) with by the mixed type of two types of the PAUR polymeric polyisocyanate of formula shown in (ii).
(annotate: above R, R ', R " be alkyl or phenyl; N is the polymerization degree, n 〉=2.)
Formula (i) and formula (ii) the polyester polyether-polyurethane polyisocyanate of mixed type are to be got by polyester polyol, polyether glycol and excessive polyisocyanate compound reaction modifying.
Advantage of the present invention and effect:
Tackiness agent of the present invention is the mixed type of two types of polyether(poly)urethane polymeric polyisocyanate and PAUR polymeric polyisocyanates, be a kind of single-component and be solvent-free tackiness agent, the characteristics that the bonding strength of existing polyester-polyurethane is high, the high hydrolysis resistance that polyether-polyurethane is arranged again, and caking agent of the present invention can be coated with compound under 40-50 ℃ of low temperature, in addition because organic solvent-free, so use pollution-free, therefore tackiness agent of the present invention is a kind of environment-friendly type tackiness agent, and can be in package compound more easily compound near being coated with under the envrionment temperature, it is compound to can be used in paper, common mould compound and plastic-aluminum combined, respond well.
Embodiment
Further specify characteristics of the present invention below by specific examples.
Example 1
In the four-hole reaction flask of stirring, thermometer is housed, according to a
1Polyester polyol: polyoxypropyleneglycol polyether glycol (N2000): TDI: the MDI mass ratio is 20: 60: 10: 36 feed intake.Concrete preparation process: the pure and mild N2000 polyether glycol of polyester polyols that adds metering earlier, heat temperature raising to 50～55 ℃, the TDI, the MDI that add metering carry out the modification building-up reactions, and control reaction temperature is at 80～85 ℃, behind the reaction 30min, add 0.01 part of DBTDL catalyzer, add simultaneously 2 parts 1, the agent of 4-chain expansion of succinic acid, continue reaction 30min after, add 2 parts of tackifier terpene phenolic resin TX-3 and 0.1 part of water-removal agent Benzoyl chloride, continue to begin the blowing of lowering the temperature behind the stirring reaction 10min.The final NCO% of product is 5.3%, and viscosity is 2600mPa.s, and suitable coating temperature is 40～50 ℃.
Described a
1The preparation method of polyester polyol: according to hexanodioic acid: m-phthalic acid: 1, the 2-propylene glycol: the glycol ether mol ratio is 1: 0.1: 0.8: 0.8 feeds intake, and syntheticly obtains that molecular weight is 1200, viscosity is the polyester polyol a of 1100mPa.s
1
Example 2
Reactions steps is with example 1, a that makes according to example 1
1Polyester polyol: N2000 polyether glycol: TDI: the IPDI mass ratio is 20: 70: 10: 50 feed intake, other raw material and ingredient proportion are 0.015 part of DMDEE and 0.005 part of triethylamine catalyzer, 1.5 part is to the hydroxymethyl-cyclohexane chainextender, 1.5 part TX-2 tackifier, 0.2 part of vinyltrimethoxy silane water-removal agent.The final NCO of product is 5.5%, and viscosity is 2000mPa.s, and suitable coating temperature is at 40～50 ℃.
Example 3
Reactions steps is with example 1, according to a
2Polyester polyol: 330N polyether glycol: TDI: the IPDI mass ratio is 20: 60: 10: 40 feed intake, other raw material and ingredient proportion are 0.015 part of DMDEE and 0.005 part of stannous octoate catalyst, 1.0 part to hydroxymethyl-cyclohexane and 1.0 part 1, the agent of 4-chain expansion of succinic acid, 1.0 part TX-1 and 1.0 parts of TX-3 tackifier, 0.2 part of vinyltrimethoxy silane water-removal agent.The final NCO of product is 4.8%, and viscosity is 1500mPa.s, and suitable coating temperature is 40～50 ℃.
Described a
2The preparation process of polyester polyol: according to hexanodioic acid: sebacic acid: 2-methyl isophthalic acid, ammediol a: condensed ethandiol: 1,4-butyleneglycol mol ratio is: 1: 0.5: 1: feed intake at 0.5: 0.7, synthetic obtain that molecular weight is 950, viscosity is the polyester polyol a of 900mPa.s
2
Example 4
Reactions steps is with example 1, a that makes according to example 3
2Polyester polyol: N2000 polyether glycol: the MDI mass ratio is to feed intake at 20: 60: 56, other raw materials and ingredient proportion are 0.01 part of DMDEE and 0.005 part of DBTDL catalyzer, 0.5 part to hydroxymethyl-cyclohexane and 1.0 part 1, the agent of 4-chain expansion of succinic acid, 1.0 part TX-2 and 1.0 parts of TX-4 tackifier, 0.1 part of Benzoyl chloride water-removal agent.The final NCO of product is 5.2%, and viscosity is 2200mPa.s, and suitable coating temperature is 40～50 ℃.
Example 5
This example is an application example.
With the product (YH701-1k) of example 1 and Henkel KGaA product of the same type (UR7515) be applied to paper/polypropylene film (PP) carry out compound, correlation data such as following table 1.According to data as can be seen, this product is the same substantially with external product on adhesive effect, but the use temperature of this product is lower, the resistance to hydrolysis energy is better, cost is lower.
Table 1
| Sample | Cost (unit/kg) | Coating temperature (℃) | Adhesive effect | Resistance to hydrolysis |
| UR7515 | 40-50 | 80-100 | When peeling off, ply of paper is torn | Generally |
| YH701-1k | 20-30 | 40-50 | Better |
Claims (7)
1, a kind of low temperature coated one-component solvent-free polyurethane adhesive is characterized in that the raw material and the mass fraction thereof that are adopted are as follows:
Polyester polyol 10-30 part, polyether glycol 50-80 part, polyisocyanates 40-65 part, catalyzer 0.005-0.03 part, tackifier 0.5-2.0 part, chainextender 0.5-4.0 part, water-removal agent 0-1.5 part.
2, according to the described tackiness agent of claim 1, it is characterized in that described polyester polyol is to carry out the esterification condensation reaction by low molecular alcoholate and low molecular acid thing to make, its molecular weight is 700-1200, viscosity 800-1200mPa.s, hydroxyl value 100-120mgKOH/g.
Described low mass molecule alcohol thing comprises 1,2 one propylene glycol, glycol ether, 2-methyl isophthalic acid, ammediol, a condensed ethandiol, neopentyl glycol, 1, and the 4-butyleneglycol is at the mixture of interior two or more; Described low molecular acid thing comprises two or more mixture of oxalic acid, m-phthalic acid, sebacic acid, terephthalic acid.
3, according to the tackiness agent described in the claim 1, it is characterized in that described polyether glycol comprises any of polyoxypropyleneglycol, polyoxytrimethylene triol, Viscotrol C, polybutadiene diol, polytetrahydrofuran diol, be 1000-2000 in its molecule, viscosity is 500-1200mPa.s.
4, according to the tackiness agent described in the claim 1, it is characterized in that described polyisocyanates comprises tolylene diisocyanate, ditan-4,4 '-two cyanates, hexamethylene diisocyanate, isophorone diisocyanate are at interior any, two or more mixture.
5,, it is characterized in that described catalyzer draws together dibutyl tin laurate, N,N-Dibenzylamine, stannous octoate, triethylamine at interior any, two or more mixture according to the tackiness agent described in the claim 1.
6, according to the tackiness agent described in the claim 1, it is characterized in that described chainextender comprises 1,4-butyleneglycol, neopentyl glycol, neopentyl glycol, to hydroxymethyl-cyclohexane at interior a kind of, two or more mixture low-molecular-weight diol; Described tackifier comprise any or theys' of phenol aldehyde modified rosin or phenol aldehyde modified terpene phenolic resin mixture; Described water-removal agent comprise Benzoyl chloride, vinyltrimethoxy silane, molecular sieve powder, tolylsulfonyl isocyanic ester any, two or more mixture.
7, the preparation method of the tackiness agent described in the claim 1 is characterized in that preparation process may further comprise the steps:
The pure and mild polyether glycol of polyester polyols is joined in the reactor, be heated to 50-55 ℃, add polyisocyanates again, control reaction temperature is 80-85 ℃, react and add catalyzer and chainextender after 30 minutes, continuation reaction 30 minutes, adding tackifier, continued stirring reaction 10 minutes, the mass percent that promptly obtains molecular weight and be 8000-12000, end-NCO is that 4.5-5.5%, 30 ℃ of viscosity are the adhesive product of 1500-3000mPa.s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101048225A CN1322085C (en) | 2005-09-21 | 2005-09-21 | Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101048225A CN1322085C (en) | 2005-09-21 | 2005-09-21 | Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1740259A true CN1740259A (en) | 2006-03-01 |
| CN1322085C CN1322085C (en) | 2007-06-20 |
Family
ID=36092793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101048225A Expired - Fee Related CN1322085C (en) | 2005-09-21 | 2005-09-21 | Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1322085C (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792638A (en) * | 2010-03-16 | 2010-08-04 | 上海亚斯电气制造有限公司 | Single-component polyurethane underwater sealing self-curing waterproof anticorrosive marine glue and preparation method thereof |
| CN102108279A (en) * | 2010-12-17 | 2011-06-29 | 南宁琛驰商贸有限公司 | Moisture curable polyurethane adhesive and preparation method thereof |
| CN102167794A (en) * | 2010-02-26 | 2011-08-31 | 大日精化工业株式会社 | Polyurethane prepolymer |
| CN101597470B (en) * | 2008-06-03 | 2012-05-23 | 北京高盟燕山科技有限公司 | Solvent-free bi-component polyurethane adhesive and preparation method thereof |
| CN101724373B (en) * | 2009-11-19 | 2012-07-04 | 北京高盟新材料股份有限公司 | Preparation method of hot-melt reaction type adhesive for composite material |
| CN101747856B (en) * | 2008-12-16 | 2012-07-04 | 北京高盟新材料股份有限公司 | Method for preparing compound bonding agent and application of bonding agent |
| CN101724372B (en) * | 2009-11-19 | 2012-07-25 | 北京高盟新材料股份有限公司 | Preparation method of adhesive for solvent-free spinning composite |
| CN101787253B (en) * | 2010-01-22 | 2012-10-10 | 上海华峰超纤材料股份有限公司 | One-component solvent-free polyurethane adhesive and preparation method thereof and raw material composition |
| CN102911636A (en) * | 2012-09-26 | 2013-02-06 | 贵阳时代沃顿科技有限公司 | Double-component polyurethane adhesive, preparation method and application thereof |
| US8377508B2 (en) | 2007-06-06 | 2013-02-19 | Mitsui Chemicals, Inc. | Solventless laminating adhesive and process for production of composite film |
| CN102977836A (en) * | 2012-11-28 | 2013-03-20 | 四川汇利实业有限公司 | Environment-friendly adhesive for drug packaging composite membrane and preparation method thereof |
| CN103044646A (en) * | 2012-12-05 | 2013-04-17 | 广州秀珀化工股份有限公司 | Preparation method of single-component polyurea interlaminated binder |
| CN103173181A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Polyurethane sealant and preparation method thereof |
| CN101735763B (en) * | 2010-01-05 | 2013-07-24 | 四川大学 | Room temperature curing low-viscosity polyurethane foam adhesive and preparation method thereof |
| CN103509456A (en) * | 2013-09-09 | 2014-01-15 | 烟台德邦科技有限公司 | Preparation method of polyurethane drape adhesive |
| CN105544247A (en) * | 2016-01-25 | 2016-05-04 | 苏州印丝特纺织数码科技有限公司 | Printing adhesive for digital printing and preparation method thereof |
| CN106085334A (en) * | 2016-06-21 | 2016-11-09 | 南通高盟新材料有限公司 | A kind of high temperature resistant type non-solvent single-component polyurethane binder and preparation method thereof |
| CN106244080A (en) * | 2015-11-02 | 2016-12-21 | 上海昊誉化工有限公司 | The two-component polyurethane adhesive of a kind of highly effective flame-retardant sticks agent |
| CN106854449A (en) * | 2016-12-16 | 2017-06-16 | 北京京都大成新材料科技有限公司 | A kind of paper-plastic stick solvent-free single-component glue and preparation method thereof |
| CN108865043A (en) * | 2018-08-03 | 2018-11-23 | 广州睿腾新材料科技有限公司 | Two-component Strong Adhesive and the preparation method and application thereof |
| CN109849433A (en) * | 2018-12-29 | 2019-06-07 | 安徽省阜阳市国泰彩印包装有限公司 | A kind of packaging bag production method |
| CN110437785A (en) * | 2019-07-31 | 2019-11-12 | 东莞市澳中电子材料有限公司 | A kind of lithium electrit plastic film two-component polyurethane adhesive and preparation method thereof |
| CN110564352A (en) * | 2018-06-06 | 2019-12-13 | 湖北文理学院 | Improved polyurethane and preparation method thereof |
| CN112920761A (en) * | 2021-03-30 | 2021-06-08 | 湖南盛天新材料有限公司 | Environment-friendly two-component polyurethane lawn adhesive with high initial adhesion and easy construction and preparation method thereof |
| CN113773784A (en) * | 2021-08-31 | 2021-12-10 | 长春艾德斯新材料有限公司 | Composition of high-strength moisture-heat-resistant polyurethane adhesive and preparation method and application thereof |
| CN113956805A (en) * | 2021-11-09 | 2022-01-21 | 合肥中科凯辰新材料有限公司 | Single-component polyurethane composite polymer waterproof coiled material, and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11124560A (en) * | 1997-10-27 | 1999-05-11 | Toyo Ink Mfg Co Ltd | Reactive hot-melt adhesive |
| JPH11263963A (en) * | 1998-03-17 | 1999-09-28 | Konishi Co Ltd | One-pack type moisture-curable urethane liquid type adhesive composition |
| JP2003096428A (en) * | 2001-09-26 | 2003-04-03 | Dainippon Ink & Chem Inc | Solvent less adhesive composition for laminate |
-
2005
- 2005-09-21 CN CNB2005101048225A patent/CN1322085C/en not_active Expired - Fee Related
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679831B (en) * | 2007-06-06 | 2013-08-14 | 三井化学株式会社 | Solventless laminating adhesive and process for production of composite film |
| US8377508B2 (en) | 2007-06-06 | 2013-02-19 | Mitsui Chemicals, Inc. | Solventless laminating adhesive and process for production of composite film |
| CN101597470B (en) * | 2008-06-03 | 2012-05-23 | 北京高盟燕山科技有限公司 | Solvent-free bi-component polyurethane adhesive and preparation method thereof |
| CN101747856B (en) * | 2008-12-16 | 2012-07-04 | 北京高盟新材料股份有限公司 | Method for preparing compound bonding agent and application of bonding agent |
| CN101724373B (en) * | 2009-11-19 | 2012-07-04 | 北京高盟新材料股份有限公司 | Preparation method of hot-melt reaction type adhesive for composite material |
| CN101724372B (en) * | 2009-11-19 | 2012-07-25 | 北京高盟新材料股份有限公司 | Preparation method of adhesive for solvent-free spinning composite |
| CN101735763B (en) * | 2010-01-05 | 2013-07-24 | 四川大学 | Room temperature curing low-viscosity polyurethane foam adhesive and preparation method thereof |
| CN101787253B (en) * | 2010-01-22 | 2012-10-10 | 上海华峰超纤材料股份有限公司 | One-component solvent-free polyurethane adhesive and preparation method thereof and raw material composition |
| CN102167794A (en) * | 2010-02-26 | 2011-08-31 | 大日精化工业株式会社 | Polyurethane prepolymer |
| TWI508988B (en) * | 2010-02-26 | 2015-11-21 | Dainichiseika Color Chem | Amine ester prepolymer |
| CN102167794B (en) * | 2010-02-26 | 2015-05-06 | 大日精化工业株式会社 | Polyurethane prepolymer |
| CN101792638A (en) * | 2010-03-16 | 2010-08-04 | 上海亚斯电气制造有限公司 | Single-component polyurethane underwater sealing self-curing waterproof anticorrosive marine glue and preparation method thereof |
| CN102108279A (en) * | 2010-12-17 | 2011-06-29 | 南宁琛驰商贸有限公司 | Moisture curable polyurethane adhesive and preparation method thereof |
| CN102108279B (en) * | 2010-12-17 | 2013-11-27 | 广西南宁齐顺化工有限公司 | Moisture curable polyurethane adhesive and preparation method thereof |
| CN102911636B (en) * | 2012-09-26 | 2013-12-18 | 贵阳时代沃顿科技有限公司 | Double-component polyurethane adhesive, preparation method and application thereof |
| CN102911636A (en) * | 2012-09-26 | 2013-02-06 | 贵阳时代沃顿科技有限公司 | Double-component polyurethane adhesive, preparation method and application thereof |
| CN102977836A (en) * | 2012-11-28 | 2013-03-20 | 四川汇利实业有限公司 | Environment-friendly adhesive for drug packaging composite membrane and preparation method thereof |
| CN103044646A (en) * | 2012-12-05 | 2013-04-17 | 广州秀珀化工股份有限公司 | Preparation method of single-component polyurea interlaminated binder |
| CN103044646B (en) * | 2012-12-05 | 2015-04-15 | 广州秀珀化工股份有限公司 | Preparation method of single-component polyurea interlaminated binder |
| CN103173181A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Polyurethane sealant and preparation method thereof |
| CN103173181B (en) * | 2013-03-23 | 2014-12-03 | 广东新展化工新材料有限公司 | Polyurethane sealant and preparation method thereof |
| CN103509456A (en) * | 2013-09-09 | 2014-01-15 | 烟台德邦科技有限公司 | Preparation method of polyurethane drape adhesive |
| CN103509456B (en) * | 2013-09-09 | 2015-06-10 | 烟台德邦科技有限公司 | Preparation method of polyurethane drape adhesive |
| CN106244080A (en) * | 2015-11-02 | 2016-12-21 | 上海昊誉化工有限公司 | The two-component polyurethane adhesive of a kind of highly effective flame-retardant sticks agent |
| CN105544247A (en) * | 2016-01-25 | 2016-05-04 | 苏州印丝特纺织数码科技有限公司 | Printing adhesive for digital printing and preparation method thereof |
| CN105544247B (en) * | 2016-01-25 | 2018-10-12 | 吴雨潞 | A kind of printing adhesive and preparation method thereof for digit printing |
| CN106085334A (en) * | 2016-06-21 | 2016-11-09 | 南通高盟新材料有限公司 | A kind of high temperature resistant type non-solvent single-component polyurethane binder and preparation method thereof |
| CN106854449A (en) * | 2016-12-16 | 2017-06-16 | 北京京都大成新材料科技有限公司 | A kind of paper-plastic stick solvent-free single-component glue and preparation method thereof |
| CN110564352A (en) * | 2018-06-06 | 2019-12-13 | 湖北文理学院 | Improved polyurethane and preparation method thereof |
| CN108865043A (en) * | 2018-08-03 | 2018-11-23 | 广州睿腾新材料科技有限公司 | Two-component Strong Adhesive and the preparation method and application thereof |
| CN109849433A (en) * | 2018-12-29 | 2019-06-07 | 安徽省阜阳市国泰彩印包装有限公司 | A kind of packaging bag production method |
| CN110437785A (en) * | 2019-07-31 | 2019-11-12 | 东莞市澳中电子材料有限公司 | A kind of lithium electrit plastic film two-component polyurethane adhesive and preparation method thereof |
| CN112920761A (en) * | 2021-03-30 | 2021-06-08 | 湖南盛天新材料有限公司 | Environment-friendly two-component polyurethane lawn adhesive with high initial adhesion and easy construction and preparation method thereof |
| CN113773784A (en) * | 2021-08-31 | 2021-12-10 | 长春艾德斯新材料有限公司 | Composition of high-strength moisture-heat-resistant polyurethane adhesive and preparation method and application thereof |
| CN113956805A (en) * | 2021-11-09 | 2022-01-21 | 合肥中科凯辰新材料有限公司 | Single-component polyurethane composite polymer waterproof coiled material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1322085C (en) | 2007-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1322085C (en) | Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process | |
| US10400145B2 (en) | Latent two-part polyurethane adhesives cured with infrared radiation | |
| EP3562853B1 (en) | Two-component polyurethane adhesive | |
| CN101787253B (en) | One-component solvent-free polyurethane adhesive and preparation method thereof and raw material composition | |
| CN101319129A (en) | Single-component solvent-free damp solidifying polyurethane adhesion agent and method of producing the same | |
| CN107660218A (en) | The bi-component polyurethane carbamate adhesive prepared using the isocyanate-terminated quasi-prepolymer based on poly- (epoxy butane) | |
| BRPI0907091A2 (en) | Three-component adhesive composition, method for using the three-component adhesive, use of the three-component adhesive, article, and method for improving the performance of an adhesive under different temperature. | |
| CN102585751A (en) | Adhesive compositions | |
| WO2008153668A2 (en) | Dry-to-the-touch anaerobically curable compositions and products made therefrom | |
| CN105315949B (en) | One kind has very short open hour and elastomeric adhesive for polyurethane and its application | |
| CN102585750A (en) | Adhesive compositions | |
| CN102203207B (en) | Dry-to-the-touch moisture-curable compositions and products made therefrom | |
| US7985479B2 (en) | Polyisocyanate mixtures, processes for preparing the same and uses therefor | |
| CN111763299A (en) | High-strength single-component polyurea and preparation method thereof | |
| WO2024152495A1 (en) | Hydroxyl composition for preparing bio-based polyurethane and bio-based polyurethane | |
| EP2062927B1 (en) | 2K-PU adhesive for low temperature applications | |
| JPS6131418A (en) | Moisture-curing polyurethane composition | |
| CN111171774B (en) | Reactive hot melt adhesive composition | |
| MX2013007046A (en) | Composition and process for producing a lamination adhesive for flexible packaging, and thus produced adhesive. | |
| JPH09324167A (en) | Solventless type primer composition | |
| TW200413426A (en) | Solvent-free moisture-curable hot melt urethane resin composition | |
| CN116987475B (en) | Pressure-maintaining-free and fast-curing polyurethane adhesive and preparation method thereof | |
| JPS63154717A (en) | Novel isocyanate prepolymer | |
| CN117887407B (en) | Solvent-free polyurethane adhesive with high drying speed | |
| JP4525963B2 (en) | Primer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: BEIJING COMENS NEW MATERIALS CO., LTD. Free format text: FORMER NAME: BEIJING COMENS CHEMICAL CO LTD |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 102502 Yanshan Industrial Zone, Beijing, No. 8, No. Patentee after: Beijing Comens New Materials Co., Ltd. Address before: 102502 Yanshan Industrial Zone, Beijing, No. 8, No. Patentee before: Beijing Comens Chemical Co., Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: NANTONG COMENS NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: BEIJING COMENS NEW MATERIALS CO., LTD. Effective date: 20130325 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 102502 FANGSHAN, BEIJING TO: 226407 NANTONG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130325 Address after: 226407 foreign chemical industry park, Nantong, Jiangsu Patentee after: Nantong Gaomeng New Material Co., Ltd. Address before: 102502 Yanshan Industrial Zone, Beijing, No. 8, No. Patentee before: Beijing Comens New Materials Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070620 Termination date: 20170921 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |