CN101649172A - Bonding adhesive for leather, preparation method thereof and application of bonding adhesive in leather making process - Google Patents
Bonding adhesive for leather, preparation method thereof and application of bonding adhesive in leather making process Download PDFInfo
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- CN101649172A CN101649172A CN200910112430A CN200910112430A CN101649172A CN 101649172 A CN101649172 A CN 101649172A CN 200910112430 A CN200910112430 A CN 200910112430A CN 200910112430 A CN200910112430 A CN 200910112430A CN 101649172 A CN101649172 A CN 101649172A
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- 239000010985 leather Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000853 adhesive Substances 0.000 title abstract description 8
- 230000001070 adhesive effect Effects 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 74
- 229920002545 silicone oil Polymers 0.000 claims abstract description 43
- -1 (methyl) n-butyl Chemical group 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 34
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 150000002431 hydrogen Chemical class 0.000 claims description 35
- 239000003292 glue Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical class OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012875 nonionic emulsifier Substances 0.000 claims description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 5
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012661 block copolymerization Methods 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 239000002313 adhesive film Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000004017 vitrification Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a leather bonding adhesive, a preparation method thereof and application of the bonding adhesive in the leather making process. By adopting a molecule design method, the invention grafts (methyl) n-butyl acrylate with a flexible molecular chain and a polar group to silicone oil, introduces a polar functional monomer to a silicone oil molecular chain so as to obtain a modified compound monomer, a side chain of which is provided with carboxyl, and improve the adhesive force of the silicone oil on materials; meanwhile, the oil slick phenomenon which is common in silicon-acrylic emulsion is avoided, the problem that silicone oil slicks out of common silicon-acrylic emulsion to influence the bonding strength is solved, the internal plasticization is carried out successfully, the vitrification temperature is reduced and the low-temperature flexibility of an adhesive film is increased. Meanwhile, through block copolymerization of Acrylonitrile, the invention overcomesthe defects of no oil resistance and no high temperature resistance of the conventional silicon-acrylic emulsion. Through adjusting the ratio of a soft monomer to a hard monomer and the consumption and the mode of an emulsifying agent, the invention ensures that the composite indicator reaches the optimal value, which cannot be achieved by the common silicon-acrylic emulsion.
Description
Technical field
The present invention relates to a kind of adhesive area, particularly a kind of leather sticks with glue agent and preparation method thereof and the application in leather-making technology.
Background technology
The solvent borne polyurethane solid is used in the applying of tradition leatheroid and synthetic leather backing cloth usually, but owing to discharge a large amount of organic solvents when using, is subjected to the restriction of environment decree, becomes superseded kind gradually.The aqueous polyurethane solid of immediate development though reached environmental requirement, also exists to cost an arm and a leg many deficiencies such as not water-fast not anti-solvent.
Therefore the moderate relatively acrylic ester emulsion of price has caused investigator's extensive attention.But its hot sticky cold crisp and not grease-proof congenital defect limit its further use range.At the characteristics of acrylic ester emulsion hot sticky cold crisp, the more organosilicon material of selecting for use of investigator is as properties-correcting agent both at home and abroad.Because it is good that organosilicon has the low temperature kindliness, surface tension is low, advantages such as good biocompatibility, but have that the emulsification difficulty is big, oil slick is many, mechanical strength is low and follow the shortcoming of property difference.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and a kind of compliance with environmental protection requirements is provided, moderate cost, the leather that bonding strength is good sticks with glue agent.
Another object of the present invention also is to provide a kind of method that leather sticks with glue agent for preparing.
Another object of the present invention also is to provide a kind of leather to stick with glue the application of agent in leather-making technology.
Leather of the present invention sticks with glue agent, the quaternary segmented copolymer that constitutes by hard monomer, soft monomer and functional monomer, described soft monomer is containing hydrogen silicone oil n-butyl acrylate compound monomer or containing hydrogen silicone oil n-BMA compound monomer, described hard monomer comprises methyl methacrylate, N-methylol acrylic acid amides, and described functional monomer is an acrylonitrile.
The present invention leather sticks with glue soft monomer in the agent and the ratio of hard monomer is preferably 1-1.5: 0.5-0.8.
Ratio the best of soft monomer and hard monomer is 1: 0.6.
The acrylonitrile that the present invention's leather sticks with glue in the agent accounts for monomer total amount 3-8%.
Acrylonitrile accounts for monomer total amount 5% for best.
The method that sticks with glue agent of removing from office for preparing of the present invention, (1) is preparation containing hydrogen silicone oil n-butyl acrylate compound monomer, or containing hydrogen silicone oil n-BMA compound monomer: in reaction unit, add a spot of ethanol, or toluene, 10～20 parts of Methyl Hydrogen Polysiloxane Fluids and trace palladium charcoal particle, logical nitrogen 10-15 minute, the beginning heated and stirred, be warmed up to 130-135 ℃, begin to drip n-BMA, or 200～500 parts of n-butyl acrylates, about 1h drips, isothermal reaction 10 hours, after reaction stopped, remaining positive butyl ester was reclaimed in underpressure distillation, cooling, stand-by;
(2) polymerization of quarternary copolymerized containing hydrogen silicone oil acrylate: with containing hydrogen silicone oil n-butyl acrylate or 20～30 parts of containing hydrogen silicone oil n-BMAs, 15～30 parts of methyl methacrylates, 5～10 parts of methacrylic acids, 5～10 parts of N-methylol acrylic acid amides, 1～5 part of compound emulsifying agent, deionized water, put into reactor, fully stir, it is not stratified to make emulsion reach 0.5h, stand-by; 1/3 of 20% and initiator solution of pre-emulsion put into reactor, be warming up to 80-85 ℃ slowly, when treating that blue light appears in emulsion, be incubated 0.5 hour, be cooled to 75 ℃ and drip the acrylonitrile monomer, last 1h, be warming up to 80-85 ℃ again, begin to drip residual monomer and initiator solution, drip off in the 3h, be incubated 1 hour, reduce to room temperature, transfer pH value 7-8, make the containing hydrogen silicone oil acrylate copolymer emulsion.
Described compound emulsifying agent is for using the composite pre-emulsifying agent of the moon/nonionic emulsifier.
Along with the ratio increase of non-/ anionic emulsifier, the cohesion rate is the back increase that descends, and when its ratio reached 1.5: 1.0, the synergy of the two reached optimum value, cohesion rate minimum, and polymerization stability is best.
Described compound emulsifying agent is a polyoxyethylene nonylphenol ether, the mixture of sodium lauryl sulphate.
The ratio of described polyoxyethylene nonylphenol ether and sodium lauryl sulphate is that 1.5: 1.0 effects are best.
In the preparation building-up reactions of containing hydrogen silicone oil (methyl) n-butyl acrylate compound monomer, (seeing accompanying drawing) seen from the proton magnetic spectrum of synthetic product, and the characteristic peak of Si-H disappears substantially at the 4.7PPm place, can prove that also the Si-H in the containing hydrogen silicone oil disappears; 3.95ppm locate to be the continuous subunit of ester bond; Chemical shift is split the bimodal of branch at 1.91ppm, 1.82ppm two places for the influence that the methylene radical that links to each other with Si is subjected to methyne; 1.61ppm, 1.41ppm is the other two methylene radical absorption peaks in the positive butyl ester; 1.1ppm---0.8ppm be subjected to the triplet that splits branch of the influence of time methylene radical for methyl.Can prove that thus addition reaction has taken place C=C in Si-H in the containing hydrogen silicone oil and the n-BMA, has formed chemical bond, for follow-up free radical reaction provides the assurance that mixes.
Form copolymerization system with soft monomer, hard monomer, functional monomer, the fixing total amount of soft monomer, the acrylonitrile consumption is 5%, the methacrylic acid consumption is 5%, constant when identical in other component with processing condition, change of the influence of the ratio of containing hydrogen silicone oil n-BMA compound monomer and methyl methacrylate, the results are shown in Table 1 gel fraction, stripping strength and second-order transition temperature.
Table 1 changes the influence of containing hydrogen silicone oil n-BMA compound monomer NMBA-SiH/ methyl methacrylate MMA ratio to gel fraction, stripping strength and second-order transition temperature
| ??NMBA- ??SiH/MMA | ??1.0∶2.0 | ??1.0∶1.25 | ??1.0∶0.8 | ??1.0∶0.6 | ??1.0∶0.5 | ??1.0∶0.3 |
| Emulsion appearance | Milky white no blue light | Milky white no blue light | Milky white has blue light | Milky white has blue light | Milky white has blue light | Milky white has blue light |
| Gel fraction (%) | ??4.2 | ??1.6 | ??1.1 | ??0.1 | ??0.0 | ??0.0 |
| Second-order transition temperature Tg | ??10℃ | ??5℃ | ??-5℃ | ??-10℃ | ??-15℃ | ??-17℃ |
As shown in Table 1, increase along with containing hydrogen silicone oil n-BMA soft monomer, the emulsion gel rate reduces, and polymerization stability increases, and stripping strength increases, this is because the soft monomer consumption increases, the flexibility of copolymer molecule key increases, and to the wettability increase of non-polar material, adhesive power increases, stripping strength increases, and second-order transition temperature descends.After force of cohesion that the adhesive power of soft monomer contribution and hard monomer are contributed reached balance, stripping strength descended on the contrary when the soft monomer ratio was too big, and glued membrane after-tacks, and force of cohesion is not enough.So the monomeric ratio of soft or hard was best at 1: 0.6, second-order transition temperature also adheres to specification.
Adopt the composite pre-emulsification system of the moon/nonionic emulsifier, the emulsion that makes has thin, low a bubble and stable characteristics concurrently.Employing Nonyl pheno (40) ether and sodium lauryl sulphate proportioning are that 1.5: 1.0 effect is relatively good.Under the constant situation of other condition, the influence that emulsification dosage is formed emulsion property sees Table 2.
Table 2 emulsifying agent is formed the influence to emulsion property
| Non-/the anionic emulsifier ratio | ??0.5∶1.0 | ??1.0∶1.0 | ??1.5∶1.0 | ??2.0∶1.0 | ??2.5∶1.0 |
| Emulsion appearance | Milky white translucent | Milky white translucent | Milky white has blue light | Milky white translucent | Milky white opaque |
| The cohesion rate | ??12.4 | ??4.8 | ??0.2 | ??3.4 | ??8.9 |
As can be seen from Table 2, the ratio of non-/ anionic emulsifier increases, and the cohesion rate is the back increase that descends, and when its ratio reached 1.5: 1.0, the synergy of the two reached optimum value, cohesion rate minimum, and polymerization stability is best.
The consumption of acrylonitrile is to the influence of cohesion rate, stripping strength and oil-proofness
Acrylonitrile is as hard monomer, and when other component and processing condition were constant, when changing its consumption, cohesion rate, oil-proofness and stripping strength can respective change.The results are shown in Table 3
Table 3 acrylonitrile different amounts is to the influence of cohesion rate, oil-proofness and stripping strength
| The fine consumption AN of propylene (%) | ??3.0 | ??4.0 | ??5.0 | ??6.0 | ??7.0 | ??9.0 |
| Cohesion rate (%) | ??0.2 | ??0.2 | ??0.2 | ??1.1 | ??1.8 | ??3.4 |
| Stripping strength (N/cm) | ??16.98 | ??17.2 | ??20.46 | ??18.24 | ??16.63 | ??16.25 |
| Butanone swelling time (S) | ??10 | ??20 | ??35 | ??48 | ??60 | ??100 |
By table 3 as seen, with the increase of acrylonitrile AN consumption, though oil-proofness can be better, the cohesion rate can not be directly proportional with stripping strength.When the AN consumption was 5%, it is maximum that stripping strength reaches, but the AN consumption can make the molecular polarity of polymkeric substance excessive when increasing, and causes stripping strength to reduce, and the cohesion rate also can increase.Consider the combined influence of AN consumption, decide the AN consumption and account for the about 5.0% best of monomer total amount.
Leather of the present invention sticks with glue agent and like product technical performance index to when analyzing
Table 5 like product technical indicator performance comparison
We are not difficult to find out from table 5.The overall target of product innovation BPA-09 and physico-chemical property obviously are better than other two kinds of like products.According to intelligence analysis, because environmental protection, investigators are partial to the modification of aqueous polyurethane and acrylic ester emulsion mostly, though breakthrough is arranged technically,, rarely have finding at leather with the specialty progress then both at home and abroad more.
The present invention's leather sticks with glue the application of agent in leather-making technology, and its prescription is:
1, tap water 15-20 part
2, wetting agent 0.2-0.25 part
3, defoamer 0.2-0.25 part
4, containing hydrogen silicone oil acrylic ester emulsion 65-85 part
5, weighting material (CaCO3) 20-25 part
Above-mentioned materials is dropped into the dispersion cylinder successively, starts dispersion machine in 500---1000r/min, high speed dispersion 1 hour filters and packages and is finished product, presses the 100-130g/Y applying glue, and the backing cloth that is used for the PVC leatheroid is fitted, and the sexual valence effect is very remarkable.
In sum, the invention has the advantages that:
The present invention takes molecule design method, (methyl) n-butyl acrylate that will have submissive molecular chain and have a polar group is grafted on the silicone oil, in the silicone oil molecular chain, introduce band polar functional monomer, the modification compound monomer that has carboxyl with this side chain that is resolved, improve the sticking power of silicone oil to material, avoided oil slick phenomenon common in the organosilicon crylic acid latex simultaneously, solved silicone oil emersion in the general organosilicon crylic acid latex polymerization, have influence on the problem of bonding strength, and successfully carried out internal plasticization, reduce second-order transition temperature, increased the low temperature flexibility of glued membrane.By the block copolymerization acrylonitrile, solved the not defective of oil resistant non-refractory of conventional acrylic emulsion simultaneously.The present invention is by adjusting the ratio of soft monomer and hard monomer, and the consumption of emulsifying agent and mode, makes overall target reach optimum value, for general acrylic ester emulsion can't be obtained.
Description of drawings
Fig. 1 sticks with glue the proton magnetic spectrum figure of agent for the present invention's leather
Embodiment
Below in conjunction with embodiment the present invention is described in more detail.
Embodiment 1
The first step: the producing of containing hydrogen silicone oil n-butyl acrylate compound monomer,
In the four-hole boiling flask that electronic stirring, reflux condensing tube are housed, add a spot of toluene, 12 parts of Methyl Hydrogen Polysiloxane Fluids and trace palladium charcoal particle, logical nitrogen 10 minutes, the beginning heated and stirred is warmed up to 130 ℃, 300 parts of the positive butyl esters of beginning dropwise addition of acrylic acid, about 1h drips, isothermal reaction 10 hours.After reaction stopped, remaining positive butyl ester, cooling, packed for standby use were reclaimed in underpressure distillation.
Second step: the polymerization of quarternary copolymerized containing hydrogen silicone oil acrylate
With 22 parts of containing hydrogen silicone oil n-butyl acrylates (NBMA-SiH), 18 parts of methyl methacrylates (MMA), 6 parts of methacrylic acids (MAA), 8 parts of N-methylol acrylic acid amides (NMA), 4 parts-union of compound emulsifying agent base phenol polyethenoxy ether (NP-40) and sodium lauryl sulphate (K12) were in 1.5: 1.0 ratio proportioning, deionized water, put into reactor, fully stir, it is not stratified to make emulsion reach 0.5h.The suction header tank is stand-by then.
1/3 of 20% and the initiator solution (Potassium Persulphate) of pre-emulsion put into reactor, be warming up to 82 ℃ slowly, when treating that blue light appears in emulsion, be incubated 0.5 hour, be cooled to 75 ℃ and drip the acrylonitrile monomer, last 1h, be warming up to 82 ℃ again, begin to drip residual monomer and initiator solution, drip off in the 3h, be incubated 1 hour, reduce to room temperature, transfer pH value 7-8, make the containing hydrogen silicone oil acrylate copolymer emulsion.
Make the quaternary segmented copolymer that constitutes by hard monomer, soft monomer and functional monomer through aforesaid method, described soft monomer is a containing hydrogen silicone oil n-butyl acrylate compound monomer, described hard monomer comprises methyl methacrylate, N-methylol acrylic acid amides, and described functional monomer is an acrylonitrile.
It is same as the prior art that present embodiment is not stated part.
Embodiment 2
Embodiment 1
The first step: the producing of containing hydrogen silicone oil n-BMA compound monomer,
In the four-hole boiling flask that electronic stirring, reflux condensing tube are housed, add a spot of ethanol, 15 parts of Methyl Hydrogen Polysiloxane Fluids and trace palladium charcoal particle, logical nitrogen 10 minutes, the beginning heated and stirred, be warmed up to 130 ℃, begin to drip 400 parts of n-BMAs, about 1h drips, isothermal reaction 10 hours.After reaction stopped, remaining positive butyl ester, cooling, packed for standby use were reclaimed in underpressure distillation.
Second step: the polymerization of quarternary copolymerized containing hydrogen silicone oil acrylate
With 28 parts of containing hydrogen silicone oil n-BMAs (NBMA-SiH), 28 parts of methyl methacrylates (MMA), 6 parts of methacrylic acids (MAA), 6 parts of N-methylol acrylic acid amides (NMA), 2 parts-compound emulsifying agent of compound emulsifying agent, 4 parts-union base phenol polyethenoxy (40) ether (NP-40) and sodium lauryl sulphate (K12) were in 1.5: 1.0 ratio proportioning, deionized water, put into reactor, fully stir, it is not stratified to make emulsion reach 0.5h.The suction header tank is stand-by then.
1/3 of 20% and the initiator solution (ammonium persulphate) of pre-emulsion put into reactor, be warming up to 81 ℃ slowly, when treating that blue light appears in emulsion, be incubated 0.5 hour, be cooled to 75 ℃ and drip the acrylonitrile monomer, last 1h, be warming up to 81 ℃ again, begin to drip residual monomer and initiator solution, drip off in the 3h, be incubated 1 hour, reduce to room temperature, transfer pH value 7-8, make the containing hydrogen silicone oil acrylate copolymer emulsion.
Make the quaternary segmented copolymer that constitutes by hard monomer, soft monomer and functional monomer through aforesaid method, described soft monomer is a containing hydrogen silicone oil n-BMA compound monomer, described hard monomer comprises methyl methacrylate, N-methylol acrylic acid amides, and described functional monomer is an acrylonitrile.
It is same as the prior art that present embodiment is not stated part.
Embodiment 3
The present invention's leather sticks with glue the application of agent in leather-making technology, and its prescription is:
1, tap water is 18 parts
2, wetting agent is 0.22 part
3, defoamer is 0.22 part
4, the containing hydrogen silicone oil acrylic ester emulsion is 75 parts
5, weighting material (CaCO3) is 22 parts
Above-mentioned materials is dropped into the dispersion cylinder successively, start dispersion machine in 500-1000r/min, high speed dispersion 1 hour filters and packages and is finished product, presses the 100-130g/Y applying glue, and the backing cloth that is used for the PVC leatheroid is fitted.
Claims (10)
1. a leather sticks with glue agent, its quaternary segmented copolymer for constituting by hard monomer, soft monomer and functional monomer, described soft monomer is containing hydrogen silicone oil n-butyl acrylate compound monomer or containing hydrogen silicone oil n-BMA compound monomer, described hard monomer comprises methyl methacrylate, N-methylol acrylic acid amides, and described functional monomer is an acrylonitrile.
2. leather according to claim 1 sticks with glue agent, it is characterized in that: described leather sticks with glue soft monomer in the agent and the ratio of hard monomer is 1-1.5: 0.5-0.8.
3. leather according to claim 2 sticks with glue agent, it is characterized in that: the ratio of soft monomer and hard monomer is 1: 0.6.
4. leather according to claim 3 sticks with glue agent, it is characterized in that: the acrylonitrile that described leather sticks with glue in the agent accounts for monomer total amount 3-8%.
5. leather according to claim 4 sticks with glue agent, it is characterized in that: acrylonitrile accounts for monomer total amount 5%.
6. a leather for preparing claim 1 sticks with glue the method for agent, (1) preparation containing hydrogen silicone oil n-butyl acrylate compound monomer, or containing hydrogen silicone oil n-BMA compound monomer: in reaction unit, add a spot of ethanol, or toluene, 10～20 parts of Methyl Hydrogen Polysiloxane Fluids and trace palladium charcoal particle, logical nitrogen 10-15 minute, the beginning heated and stirred, be warmed up to 130-135 ℃, begin to drip n-BMA, or 200～500 parts of n-butyl acrylates, about 1h drips, isothermal reaction 10 hours, after reaction stopped, remaining positive butyl ester was reclaimed in underpressure distillation, cooling, stand-by;
(2) polymerization of quarternary copolymerized containing hydrogen silicone oil acrylate: with containing hydrogen silicone oil n-butyl acrylate or 20～30 parts of containing hydrogen silicone oil n-BMAs, 15～30 parts of methyl methacrylates, 5～10 parts of methacrylic acids, 5～10 parts of N-methylol acrylic acid amides, 1～5 part of compound emulsifying agent, deionized water, put into reactor, fully stir, it is not stratified to make emulsion reach 0.5h, stand-by; 1/3 of 20% and initiator solution of pre-emulsion put into reactor, be warming up to 80-85 ℃ slowly, when treating that blue light appears in emulsion, be incubated 0.5 hour, be cooled to 75 ℃ and drip the acrylonitrile monomer, last 1h, be warming up to 80-85 ℃ again, begin to drip residual monomer and initiator solution, drip off in the 3h, be incubated 1 hour, reduce to room temperature, transfer pH value 7-8, make the containing hydrogen silicone oil acrylate copolymer emulsion.
7. remove from office the method that sticks with glue agent according to claim 6 the preparation, it is characterized in that: described compound emulsifying agent is for using the composite pre-emulsifying agent of the moon/nonionic emulsifier.
8. remove from office the method that sticks with glue agent according to claim 7 the preparation, and it is characterized in that: described compound emulsifying agent is a polyoxyethylene nonylphenol ether, the mixture of sodium lauryl sulphate.
9. remove from office the method that sticks with glue agent according to claim 8 the preparation, and it is characterized in that: the ratio of described polyoxyethylene nonylphenol ether and sodium lauryl sulphate is that 1.5: 1.0 effects are best.
10. leather as claimed in claim 1 sticks with glue the application of agent in leather-making technology, its prescription is for by weight: tap water 15-20 part, wetting agent 0.2-0.25 part, defoamer 0.2-0.25 part, containing hydrogen silicone oil acrylic ester emulsion 65-85 part weighting material (CaCO3) 20-0.25 part, above-mentioned materials is dropped into the dispersion cylinder successively, start dispersion machine in 500-1000r/min, high speed dispersion 1 hour filters and packages and is finished product, press the 100-130g/Y applying glue, the backing cloth that is used for the PVC leatheroid is fitted.
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| CN2009101124301A CN101649172B (en) | 2009-08-26 | 2009-08-26 | Bonding adhesive for leather, preparation method thereof and application of bonding adhesive in leather making process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396741A (en) * | 2013-07-25 | 2013-11-20 | 湖北大学 | Zero-VOC (Volatile Organic Compounds) photo-polymer acrylate pressure-sensitive adhesive composition and preparation method thereof |
| CN111635659A (en) * | 2020-06-22 | 2020-09-08 | 广东金能建筑节能材料科技有限公司 | Flame-retardant water-resistant sound-insulation coating and preparation method thereof |
| CN117809893A (en) * | 2024-01-09 | 2024-04-02 | 南网电缆(广州)有限公司 | Corrosion-resistant new energy automobile charging cable and preparation method thereof |
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2009
- 2009-08-26 CN CN2009101124301A patent/CN101649172B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396741A (en) * | 2013-07-25 | 2013-11-20 | 湖北大学 | Zero-VOC (Volatile Organic Compounds) photo-polymer acrylate pressure-sensitive adhesive composition and preparation method thereof |
| CN103396741B (en) * | 2013-07-25 | 2015-01-21 | 湖北大学 | Zero-VOC (Volatile Organic Compounds) photo-polymer acrylate pressure-sensitive adhesive composition and preparation method thereof |
| CN111635659A (en) * | 2020-06-22 | 2020-09-08 | 广东金能建筑节能材料科技有限公司 | Flame-retardant water-resistant sound-insulation coating and preparation method thereof |
| CN117809893A (en) * | 2024-01-09 | 2024-04-02 | 南网电缆(广州)有限公司 | Corrosion-resistant new energy automobile charging cable and preparation method thereof |
| CN117809893B (en) * | 2024-01-09 | 2024-06-04 | 南网电缆(广州)有限公司 | Corrosion-resistant new energy automobile charging cable and preparation method thereof |
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| CN101649172B (en) | 2012-01-18 |
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