CN1257950C - Boiling resistant polyurethane adhesive and method for preparing same - Google Patents
Boiling resistant polyurethane adhesive and method for preparing same Download PDFInfo
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- CN1257950C CN1257950C CN200410067662.7A CN200410067662A CN1257950C CN 1257950 C CN1257950 C CN 1257950C CN 200410067662 A CN200410067662 A CN 200410067662A CN 1257950 C CN1257950 C CN 1257950C
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- Prior art keywords
- acid
- polyurethane adhesive
- resistant polyurethane
- alcohol
- boiling resistant
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- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 238000009835 boiling Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 229920000728 polyester Polymers 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 229920005906 polyester polyol Polymers 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000007520 diprotic acids Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 6
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000005057 Hexamethylene 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 8
- 238000010025 steaming Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 235000013305 food Nutrition 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 5
- 238000012856 packing Methods 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract description 3
- 238000004026 adhesive bonding Methods 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000005030 aluminium foil Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229940100573 methylpropanediol Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002631 hypothermal effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention discloses a boiling resistant polyurethane adhesive and a preparation method thereof. The boiling resistant polyurethane adhesive is bi-component adhesive. The boiling resistant polyurethane adhesive comprises 50 to 90 mass% of main agent and 10 to 50 mass% of solidifying agent, wherein the main agent comprises (A) polyether ester polyhydric alcohol whose hydroxyl value is from 10 to 30 mgKOH/g and (B) polyester polyhydric alcohol whose hydroxyl value is from 30 to 100 mgKOH/g; the solidifying agent is a polyisocyanate prepolymer. The boiling resistant polyurethane adhesive can be applied to an intaglio plate gluing dry type composite machine. A product after being compounded has very high initial bonding strength, and can be used for lower slitting and bag making working procedures after the product is slaked more than 48 hours under the environment of 50(+/-)5 DEG C. The boiling resistant polyurethane adhesive is required to be further placed more than 7 days at normal temperature before the boiling resistant polyurethane adhesive is steamed. The product has very high bonding strength to the compounding of aluminum and plastics, and has the advantages of sanitation, excellent moisture and heat resistance, excellent chemical medium resistance and excellent low temperature resistance. The present invention relates to the adhesive which is particularly suitable for the processing of high temperature steaming bags for food packing of soft package industry.
Description
Technical field
The present invention relates to a kind of boiling resistant polyurethane adhesive.Be specifically related to a kind of by (A) the high branched polyester polyvalent alcohol (hydroxyl value 30-100mgKOH/g) and (C) polyurethane adhesive formed of polyisocyanate prepolymers of linear or low branch polyether ester polyol (hydroxyl value 5-30mgKOH/g), (B) low relative molecular mass of low or medium relative molecular mass.
Background technology
In recent years, along with improving constantly of people's living standard, to the also raising day by day of packing instructions of various food.For the wholesomeness and the quality guaranteed period of improving food, comprise two-layer or two-layer more than film not of the same race, have more fully that the composite membrane of physics and chemical property is widely used.Fish, cooked meat for instant bagged, its requirement to packing is higher, normally adopting has the composite structure of high barrier to oxygen and moisture, and also will carry out quality guaranteed period and the shelf-life of the high temperature steaming process killing microorganisms of certain hour with prolongation food behind the packing envelope.The soft packaging industry claims the packing bag of this structure to be " pressure pad ".The high request of pressure pad embodies both ways, and the first adopts one or more layers of high barrier film, and as aluminium foil, polyester or nylon membrane etc., aluminium foil especially is because it almost is that " zero " permeates to gas and moisture; Another is the tackiness agent of compound employing, and it must be competent at the process of high temperature steaming, is unlikely to make behind high temperature steaming adhesion failure, and when freezing preservation embrittlement not.High-temperature cooking process divides two kinds, a kind of be 120 ℃ following 30 minutes, another kind be 135 ℃ following 30 minutes.The polyurethane adhesive that the present invention relates to can be competent at a kind of technology in back, and the deep hypothermia that can stand below-20 ℃ is freezing.
Forefathers' work has to relate to and is used for film compound polyurethane adhesive.Wherein, USP4206299, EP 349839 etc. disclose the technology of anti-135 ℃ of high temperature steaming polyurethane composite gel sticks; CN 1232851A, CN 1355268A etc. disclose the technology of anti-120 ℃ of high temperature steaming polyurethane composite gel sticks; CN 1316480A discloses the technology that can effectively improve the polyurethane composite gel stick of the bonding performance of aluminium plating film.These patents do not relate to the molecular designing technology based on polyether ester, there is not that withstands deep freezing performance with respect to tackiness agent yet, therefore described patent can not satisfy people's application requiring in the defective that is applied to also exist low temperature to perform poor when deep-frozen goods is packed.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of boiling resistant polyurethane adhesive and preparation method thereof, to overcome the above-mentioned defective that prior art exists, satisfy people's needs.
Boiling resistant polyurethane adhesive of the present invention, the polyurethane adhesive for a kind of high-crosslinking-degree, molecular structure have multiple block characteristic is a kind of two component adhesive, comprises that mass percentage content is the host of 50-90% and the solidifying agent of 10-50%;
Said host by (A) hydroxyl value be the polyester ether polylol of 10-30mgKOH/g and (B) hydroxyl value be that the polyester polyol of 30-100mgKOH/g is formed;
(A) mass content of component is 50-80%
(B) mass content of component is 20-50%;
Said solidifying agent is a polyisocyanate prepolymers.
(A) polyether block in the component gives tackiness agent pliable and tough and low temperature resistant characteristic, and it has excellent in water resistance simultaneously; The high aromatised fraction content of tackiness agent then makes it possess good humidity resistance;
(B) thus the polyester polyol in the component is given the moisture-proof thermal property that the tackiness agent high crosslink density further improves tackiness agent;
Said polyisocyanate prepolymers is the reaction product of vulcabond and polyvalent alcohol, and its general structure is as follows:
R is for comprising the organic multiple-amino ester formate group of poly-hydroxy.
Preferred vulcabond is selected from one or more in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or the xylylene diisocyanate (XDI) etc.;
Preferred polyhydric alcohols is selected from a kind of or mixture in glycerine or the TriMethylolPropane(TMP) etc.;
" polyurethane adhesive " that the polyisocyanate prepolymers preparation method is few male Lee and Liu Yijun writes (Chemical Industry Press, P121) in existing open report, or employing commercially available prod; Wherein vulcabond is excessive, this with regard to the end group that has guaranteed institute's synthetic prepolymer be isocyanate groups (NCO).Its function is to make the terminal hydroxy group of its isocyanate end and host (OH) home position polymerization reaction to take place, and the polyfunctional group characteristic of utilizing polyisocyanate prepolymers makes tackiness agent further form the structure of crosslinking net, makes laminated film have its desired thermotolerance, chemical-resistant and further improves the body intensity of tackiness agent.
Above-mentioned polyester ether polylol and polyester polyol are the terminal hydroxy group structure, the two is compatible fully, as product, be packaged in after they mix and constitute host in the same container, the polyisocyanate prepolymers that is packaged in another container is then as solidifying agent, and host and solidifying agent constitute the common bi-component polyurethane adhesive product in market jointly.No matter be host or solidifying agent, they all are dissolved in organic solvent with respective components with certain solids content and form.Wherein organic solvent must not contain reactive hydrogen, moisture content is lower than 600ppm, and the best is lower than 300ppm.This common class organic solvent comprises toluene, ethyl acetate, methylethylketone or acetone etc., preferably ethyl acetate and methylethylketone.
According to the present invention, also can add mass percent in above-mentioned adhesive formulation is the organo-silicon coupling agent of 0.1-3%, further improves the wet-hot aging performance and the bond strength of tackiness agent, and any have as structure R-Si (X)
3Organosilicon all can utilize, wherein R is C
2-C
8Low carbon chain alkyl, X be methyl or ethyl, the consumption of organo-silicon coupling agent is the 0.1-3% of adhesive quality total amount, the best is 0.5-1.5%, can adopt the commercially available prod, is the organo-silicon coupling agent of KH-560 or KH-550 as model.
Usually require polyisocyanate prepolymers excessive, promptly require ratio [NCO]/[the OH]=1-10 of amount and the amount of host hydroxylated material of the solidifying agent polyisocyanate prepolymers of tackiness agent, that even more ideal is [NCO]/[OH]=1.5-5.
The preparation method of boiling resistant polyurethane adhesive of the present invention comprises the steps:
(1) preparation of polyester ether polylol:
With polyethers, preferably polyoxyethylene glycol or polytetrahydrofuran etc.; One or more dibasic alcohol, preferably ethylene glycol, neopentyl glycol, 1,4-butyleneglycol, 2-methyl propanediol, 1,2-propylene glycol, Diethylene Glycol etc.; Two or more diprotic acid, preferably hexanodioic acid, nonane diacid, sebacic acid, terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride, naphthalene diacid etc.; One or more polyfunctionality alcohol or sour, preferably TriMethylolPropane(TMP), glycerine, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride are raw material, the synthetic temperature is 160-250 ℃, and catalyzer is selected from tetrabutyl titanate, metatitanic acid four Virahol esters, antimonous oxide, antimony acetate, tin protochloride or dibutyl tin laurate etc.;
The alcohol that feeds intake is 1.05-1.5 with the ratio of total amount of substance of acid: 1, have the feature of terminal hydroxy group structure to guarantee institute's synthetic polyester ether polylol.
Institute's synthetic polyester ether polylol can contain slight branched structure, functionality 2-3.It is outstanding to be characterised in that it has a certain amount of polyether block structure, makes the tackiness agent low temperature performance excellent, and polytetrahydrofuran block surface tension is low, good with hot sealing layer CPP film compatibility.The synthetic polyether ester has higher force of cohesion in order to make, aromatic acid should account for the 40-70% of diprotic acid total mass in the used diprotic acid, make the polyester block in the polyester ether polylol have higher softening temperature, give tackiness agent sufficiently high initial adhesion strength.When including aluminium foil layer in the composite structure, sufficiently high initial adhesion strength is crucial to recombining process, because aluminium foil intensity is low, in recombination process, can not bear very big tension force, caused aluminium foil in the compound process, almost not have tensile deformation, and compound plastics film relative deformation amount is big with it, and the deformation of this part will constantly relax behind the following machine.In this case,, just be easy to produce so-called " tunnel " phenomenon between plastic layer and the aluminium foil layer, cause quality accident if tackiness agent does not have sufficiently high initial adhesion strength.
(2) preparation of polyester polyol:
With dibasic alcohol, ethylene glycol preferably, neopentyl glycol, 1, the 4-butyleneglycol, the 2-methyl propanediol, 1,2-propylene glycol or Diethylene Glycol etc., two or more diprotic acid, hexanodioic acid preferably, nonane diacid, sebacic acid, terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride or naphthalene diacid etc., one or more polyfunctionality alcohol or sour, TriMethylolPropane(TMP) preferably, glycerine, trimellitic acid 1,2-anhydride or pyromellitic acid acid anhydride are raw material, temperature of reaction is 160-250 ℃, and catalyzer is selected from tetrabutyl titanate, metatitanic acid four Virahol esters, antimonous oxide, antimony acetate, tin protochloride or dibutyl tin laurate etc.; The alcohol that feeds intake is 1.2-2 with the ratio of total amount of substance of acid: 1, have the feature of low relative molecular mass and terminal hydroxy group structure to guarantee institute's synthetic polyester polyol.
(3) the upward preparation of glue:
Polyester ether polylol, polyester polyol are dissolved in organic solvent, and the organo-silicon coupling agent of adding 0.1-3% obtains the host of type dry polyurethane composite adhesive.When being applied to the dry type recombining process, host and solidifying agent obtain glue by above-mentioned mixed, and the blended ratio is by the hydroxyl value of host and the isocyanate value decision of solidifying agent.
The host of the type dry polyurethane composite adhesive that the present invention relates to is adjusted its viscosity by the diluting effect of organic solvent and be lower than 1000cps to room temperature with after solidifying agent mixes, and can directly apply to intaglio plate gluing dry compound machine then.
Compound tackiness agent glue spread is 3-5g/m
2, the product after compound has very high initial adhesion intensity, can be used for cutting and the bag operation of downstream after slaking under 50 ± 5 ℃ the environment is more than 48 hours.Carry out boiling and then require further to place at normal temperatures time more than 7 days.Product of the present invention has very high bond strength to plastic-aluminum combined, and health, moisture-proof heat, anti-chemical mediator and resistance to low temperature excellence, is particularly suitable for the tackiness agent of the processing of soft packaging industry food product pack high-temperature retort bag.
Embodiment
Further specify the present invention below by embodiment:
Embodiment 1
The catalyzer tin protochloride of 166g m-phthalic acid, 202g sebacic acid, 225g2-methyl propanediol, 26.8g TriMethylolPropane(TMP) and 100ppm is dropped into the three-necked bottle reactor of 1000ml; under the nitrogen protection 160-220 ℃ react to the system hydroxyl value less than 10mgKOH/g; in 220-240 ℃ of progressively decompression continuation reaction, obtaining hydroxyl value is the polyester polyol product of 80mgKOH/g then.Add the solids content of acetic acid ethyl dissolution to 49%, be labeled as " B1 ".
Embodiment 2
522.6g tolylene diisocyanate (TDI), 219g ethyl acetate are dropped into the three-necked bottle reactor, the control temperature of charge is between 60-80 ℃, drip the TriMethylolPropane(TMP) (TMP) of 134g molten state, drip the back and continue reaction 4.5 hours, obtain the solidifying agent of type dry polyurethane composite adhesive, its isocyanate group mass contg is 14.4%, solids content is 75%, is labeled as " solidifying agent 1 ".
Embodiment 3
With the 83g terephthalic acid; the 166g m-phthalic acid; 124g ethylene glycol; 156g neopentyl glycol and catalyzer tin protochloride 100ppm drop into the three-necked bottle reactor of 1000ml; react to aquifer yield at 160-220 ℃ under the nitrogen protection and reach 54g; add the 202g sebacic acid then; the 200g relative molecular mass is 1000 polytetrahydrofuran; react to moisture to go out to the greatest extent in 200-230 ℃ of continuation; then in the 200-230 ℃ of reaction 4 hours of progressively reducing pressure; last vacuum at 1-2mmHg; 230-250 ℃ is continued reaction 4 hours down; stopped reaction; with the reaction system cooling, gained polyether ester dibasic alcohol product hydroxyl value is 11.2mgKOH/g.Add the solids content of acetic acid ethyl dissolution to 49%, be labeled as " A1 ".
3 parts of A1 and 1 part of B1, and it is even to add the KH-560 coupling agent thorough mixing of 1% quality, obtains the host of polyurethane adhesive, is labeled as " host 1 ".
Embodiment 4
Adopt the synthesis technique of A1, with 166g terephthalic acid, 148g Tetra hydro Phthalic anhydride, 188g nonane diacid, 270g1,4-butyleneglycol, 135g2-methyl propanediol, 250g relative molecular mass are that to obtain polyether ester dibasic alcohol product hydroxyl value be 11.2mgKOH/g to the reaction of 1000 polytetrahydrofuran.Add the solids content of acetic acid ethyl dissolution to 49%, be labeled as " A2 ".
3 parts of A2 and 1 part of B1, and it is even to add the KH-560 coupling agent thorough mixing of 1% quality, obtains the host of polyurethane adhesive, is labeled as " host 2 ".
Embodiment 5: the synthesis technique that adopts A1,133g terephthalic acid, 116g m-phthalic acid, 202g sebacic acid, 16.3g pyromellitic acid acid anhydride, 180g1,4-butyleneglycol, 124g ethylene glycol, 200g relative molecular mass are that the polyester ether polylol product hydroxyl value that the reaction of 1000 polytetrahydrofuran obtains slight branching is 11.2mgKOH/g.Add the solids content of acetic acid ethyl dissolution to 49%, be labeled as " A3 ".
3 parts of A3 and 1 part of B1, and it is even to add the KH-560 coupling agent thorough mixing of 1% quality, obtains the host of polyurethane adhesive, is labeled as " host 3 ".
Recombining process is: the host of above embodiment is mixed obtaining corresponding type dry polyurethane composite adhesive respectively by 20: 3 mass ratio with the solidifying agent of embodiment 1, be applied to the dry type recombining process of CPP (70 μ)/AL (9 μ)/BOPET (12 μ) structure respectively, its 50 ℃ solidified 72 hours, surveyed bond strength.
The test detail of bond strength is: the compound bond strength characterizes with T type stripping strength, specimen size is 300mm * 15mm, and equipment is omnipotent powerful drawing machine, and rate of extension is 300mm/min, the gained data are 10 cell means between CPP/AL, the N/15mm of unit.
The test detail of anti-the boiling is: bag is of a size of 13cm * 17cm, and content is the acetate that meat soup adds 10% quality, at 4.5kg/cm
2Boiling 30min in the following 135 ℃ hot water of pressure observes the outward appearance of bag and also surveys bond strength, places down at 60 ℃ then and surveys bond strength in 7 days.135 ℃ of hot cookings' link is only omitted in correlated experiment.Sample size is 5 groups.
All tests the results are shown in table 1, polyurethane adhesive disclosed in this invention can be competent at 135 ℃ of high temperature steamings virus killing processes to greasy and acidic food, is fit to industry and promotes.
The feature of the various type dry polyurethane composite adhesives of table 1 and compound stripping strength
| Host | Compound stripping strength | Stripping strength after the boiling | Uncooked stripping strength |
| Embodiment 1 embodiment 2 embodiment 3 | 12.5 11.8 13.2 | 11.9 11.1 13.0 | 12.4 11.8 13.2 |
Claims (9)
1. a boiling resistant polyurethane adhesive is characterized in that, is a kind of two component adhesive, comprises that mass percentage content is the host of 50-90% and the solidifying agent of 10-50%;
Said host by (A) hydroxyl value be the polyester ether polylol of 10-30mgKOH/g and (B) hydroxyl value be that the polyester polyol of 30-100mgKOH/g is formed;
(A) mass content of component is 50-80%
(B) mass content of component is 20-50%;
Said solidifying agent is a polyisocyanate prepolymers;
Said polyisocyanate prepolymers is the reaction product of vulcabond and polyvalent alcohol.
2. boiling resistant polyurethane adhesive according to claim 1, it is characterized in that vulcabond is selected from one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or the xylylene diisocyanate; Polyvalent alcohol is selected from a kind of or mixture in glycerine or the TriMethylolPropane(TMP).
3. boiling resistant polyurethane adhesive according to claim 1 is characterized in that vulcabond is excessive.
4. boiling resistant polyurethane adhesive according to claim 1 is characterized in that, adding mass percent in tackiness agent is the organo-silicon coupling agent of 0.1-3%.
5. boiling resistant polyurethane adhesive according to claim 4 is characterized in that, the organo-silicon coupling agent structure is R-Si (X)
3, wherein R represents C
2-C
8Low carbon chain alkyl, X be methyl or ethyl, the consumption of organo-silicon coupling agent is the 0.1-3% of adhesive quality total amount.
6. prepare the method for the described boiling resistant polyurethane adhesive of claim 1, it is characterized in that, comprise the steps:
(1) preparation of polyester ether polylol:
With polyethers, one or more dibasic alcohol, two or more diprotic acid, one or more polyfunctionality alcohol or acid is raw material, the synthetic temperature is 160-250 ℃, and catalyzer is selected from tetrabutyl titanate, metatitanic acid four Virahol esters, antimonous oxide, antimony acetate, tin protochloride or dibutyl tin laurate;
(2) preparation of polyester polyol, with dibasic alcohol, two or more diprotic acid, one or more polyfunctionality alcohol or acid is raw material, temperature of reaction is 160-250 ℃, and catalyzer is selected from tetrabutyl titanate, metatitanic acid four Virahol esters, antimonous oxide, antimony acetate, tin protochloride or dibutyl tin laurate; The alcohol that feeds intake is 1.2-2 with the ratio of the total yield of acid: 1;
(3) polyester ether polylol, polyester polyol are dissolved in organic solvent, isocyanate prepolymer is dissolved in organic solvent, promptly obtains two component adhesive.
7. method according to claim 6 is characterized in that, during the preparation of polyester ether polylol, said polyethers is selected from polyoxyethylene glycol or polytetrahydrofuran; Dibasic alcohol is selected from ethylene glycol, neopentyl glycol, 1,4-butyleneglycol, 2-methyl propanediol, 1,2-propylene glycol or Diethylene Glycol; Diprotic acid select oneself diacid, nonane diacid, sebacic acid, terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride or naphthalene diacid; Polyfunctionality alcohol or acid are selected from TriMethylolPropane(TMP), glycerine, trimellitic acid 1,2-anhydride or pyromellitic acid acid anhydride, and the alcohol that feeds intake is 1.05-1.5 with the ratio of the total yield of acid: 1.
8. method according to claim 6, it is characterized in that, during the preparation of polyester polyol, dibasic alcohol is selected from ethylene glycol, neopentyl glycol, 1,4-butyleneglycol, 2-methyl propanediol, 1,2-propylene glycol or Diethylene Glycol, diprotic acid select oneself diacid, nonane diacid, sebacic acid, terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride or naphthalene diacid, polyfunctionality alcohol or acid are selected from TriMethylolPropane(TMP), glycerine, trimellitic acid 1,2-anhydride or pyromellitic acid acid anhydride.
9. method according to claim 6 is characterized in that said organic solvent is selected from toluene, ethyl acetate, methylethylketone or acetone.
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| CN1257950C true CN1257950C (en) | 2006-05-31 |
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| CN114891474B (en) * | 2022-05-17 | 2023-07-28 | 江苏华大新材料有限公司 | High-temperature-cooking double-component polyurethane adhesive and preparation method and application thereof |
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