CN1161377A - Method for preparing leather repairing agent made of polyacrylates - Google Patents
Method for preparing leather repairing agent made of polyacrylates Download PDFInfo
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- CN1161377A CN1161377A CN 97100555 CN97100555A CN1161377A CN 1161377 A CN1161377 A CN 1161377A CN 97100555 CN97100555 CN 97100555 CN 97100555 A CN97100555 A CN 97100555A CN 1161377 A CN1161377 A CN 1161377A
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- 239000010985 leather Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 11
- 229920000058 polyacrylate Polymers 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 7
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- -1 hydroxypropyl (methyl) CALCIUM ACRYLATE Chemical compound 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NALKUPWCKZNGTJ-UHFFFAOYSA-M C(C=C)(=O)[O-].OCC[Ca+] Chemical compound C(C=C)(=O)[O-].OCC[Ca+] NALKUPWCKZNGTJ-UHFFFAOYSA-M 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000002459 sustained effect Effects 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 abstract 1
- 239000011324 bead Substances 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ALGPPMNUZIZPHC-UHFFFAOYSA-N C(CO)O.CC=CC(=O)O Chemical compound C(CO)O.CC=CC(=O)O ALGPPMNUZIZPHC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A leather repairing agent acrylic acid copolymer water dispersed substance is prepared by following steps: an oil phase mixture of acrylic resin, hydrophilic agent, crosslinking agent, initiator is mixed with an aqueous solution of chain extending crosslinking agent and emulsifier with the proportion of 1:(3.7-4.2). Then suspension polymerization technology is used to make the oil phase mixture form oil beads. Warm up temp. twice of 1 h. each under the protection of nitrogen, then distil off the moisture under reduced pressure to concentrate the polymer. This method is short in process and simple in operation. The solid content of this product can be as high as 60-63% and the damaged leather after repairing with this agent is good in quality.
Description
The present invention relates to do in a kind of leather processing procedure the preparation method of the acrylic copolymer water-dispersion material of healant.
As the employed material of leather repairing agent made, require it to have outside certain thixotroping stress, also should have good physicals, as with the sympathy of tinting material, dyestuff cream, auxiliary agent wax emulsion and leather substance, so not only adhered firmly but also easy dyeing.Also require it to have good snappiness, elasticity, physical strength and heat-resisting winter hardiness and water tolerance simultaneously, could guarantee kishke feel and the good external force resistance and the ability of water under differing temps like this.
Although existing crylic acid resin hide finishes has all advantages preferably of physical strength height, ageing-resistant, fast light, water tolerance and stability, but it is relatively poor to be used for repairing the damaged effect of leather, usually the damaged degree of depth of leather surface is between 0.5-2mm, that have even darker, and the solid content of Emulsion acrylic resin only is 30%, and need smear this emulsion repeatedly could be flat with damaged benefit, and the rubber and plastic sense of dry and hard back is serious, influence the leather visual appearance, actually operating is time-consuming.
The objective of the invention is to disclose a kind of preparation method who repairs the damaged polyacrylic acid lipid leather repairing agent made of leather surface that is specifically designed to that can overcome the above-mentioned emulsion defective.
Method of the present invention in turn includes the following steps:
With the acrylic resin of 90-98% (weight), the hydrophilizing agent of 0.1-1% (weight), the linking agent of 0.5-5% (weight), the initiator of 0.5-5% (weight) is even to be mixed, and obtains oil mixture.
With the water of 97-98% (weight), the water-based chain extension-crosslinking agent of 1-2% (weight), the emulsifying agent of 0.6-1.2% (weight) is even to be mixed, and obtains the aqueous solution of agent of aquosity chain extension-crosslinking and emulsifying agent.
Adopt suspension polymerization process; with above-mentioned oil mixture 1: stir in the above-mentioned aqueous solution of 3.7-4.2; make oil mixture become the oil droplet of 1-5mm; under protection of nitrogen gas, be warming up to 60-65 ℃ of sustained reaction 1 hour; continue to be warming up to 85-90 ℃ of isothermal reaction 1 hour; afterwards, moisture is removed in underpressure distillation under 70 ℃ boiling temperature, polymkeric substance is concentrated obtain product.
Wherein used acrylic resin can be a Butyl acrylate, Ethyl acrylate, and vinylformic acid formicester etc., its optimum amount is 92-95% (weight);
Used hydrophilizing agent is the monomer that has hydrophilic radical and strong polar group, as methylol acryloyl ammonium, hydroxyethyl CALCIUM ACRYLATE, hydroxyethyl methacrylate, hydroxypropylmethyl) CALCIUM ACRYLATE, (methyl) vinylformic acid etc.;
Used linking agent can be a divinylbenzene, (methyl) vinylformic acid ethylene glycol fat, and (methyl) vinylformic acid poly binary alcohol ester, tricyanic acid three allyl fat etc., optimum amount is 1-2% (weight);
Used initiator adopts azo-initiator, and as Diisopropyl azodicarboxylate, optimum amount is 1-2% (weight);
Used water-based chain extension-crosslinking agent is a polyvinyl alcohol;
Used emulsifying agent is a sodium lauryl sulfate.
Because the present invention adopts suspension polymerization process, therefore reaction is more complete, and the solid content height.Secondary temperature elevation technology of the present invention, when promptly temperature rose to 60-65 ℃, polyreaction was carried out and is continued 1 hour, the transformation efficiency of control resin crosslinks, when temperature rises to 85-90 ℃, remaining decomposition of initiator, polyreaction stops, and discharges a large amount of nitrogen, produces bubble.Make the polymkeric substance albefaction reduce transparency, so the product good springiness strong covering power of present method acquisition, and kept the resistant to elevated temperatures characteristic of acrylic resin.
The leather repairing agent made that present method makes, carboxyl-content generally can account for the 0.1-1% of solid amount, and optimum range should be controlled between the 0.5-0.8%, so both can guarantee the particulate wetting ability, be convenient to the extruding of abutment surface tension force and form stronger cohesive force, enough water tolerance are arranged again simultaneously.Hydroxy radical content can be between 0.05-0.5%, and hydroxyl is except there being certain wetting ability, improves outside aqueous dispersion stable, also can increase intergranular reactive force, improve strength stress and dry and hard after intensity.
Embodiment: get Butyl acrylate 100g
Linking agent divinylbenzene 4g
Initiator Diisopropyl azodicarboxylate 4g
Hydrophilizing agent methacrylic acid 0.3g
Hydrophilizing agent hydroxyl second fat methacrylic acid 0.7g
Obtain oil mixture 109g behind the uniform mixing
Water intaking 400g
Water-based chain extension-crosslinking agent polyvinyl alcohol 8g
Emulsifier sodium lauryl sulfate 2.4g
Obtain aqueous phase solution 410.4g after the dissolving
Under nitrogen protection, above-mentioned oil mixture is joined in the above-mentioned aqueous phase solution; the oil droplet diameter that is stirred to oil phase is in the 1-5mm scope; be warming up to 65 ℃ and continue 1 hour; examining under a microscope oil droplet is not out of shape because of bonding; be warming up to 85 ℃ then and kept 1 hour, Diisopropyl azodicarboxylate is decomposed, remaining monomer complete reaction; in oil droplet, form micro-bubble, distillation and add trolamine and adjust pH value and promptly obtain product---leather repairing agent made to 7-8 under 70 ℃ boiling temperature.
Method flow of the present invention is short, simple to operate, and the products obtained therefrom solid content is up to 60-63%, damaged once the smearing of common leather gets final product, and be dry and hard rear except having the acrylate emulsion Various good index, performance beyond, especially have the micropore of being full of high resilience, bonding Firmly, softly do not subside, covering power is extremely strong, the remarkable advantage that kishke feel is good.
Claims (6)
1. the preparation method of polyacrylic acid lipid leather repairing agent made is characterized in that in turn including the following steps:
With the acrylic resin of 90-98% (weight), the hydrophilizing agent of 0.1-1% (weight), the linking agent of 0.5-5% (weight), even the mixing of initiator of 0.5-5% (weight), obtain oil mixture.
With the water of 97-98% (weight), the water-based chain extension-crosslinking agent of 1-2% (weight), the emulsifying agent of 0.6-1.2% (weight) are spared mixed, obtain the aqueous solution of agent of aquosity chain extension-crosslinking and emulsifying agent.
Adopt suspension polymerization process, with above-mentioned oil mixture 1: stir in the above-mentioned aqueous solution of 3.7-4.2; Make oil mixture become the oil droplet of 1-5 μ m; under protection of nitrogen gas, be warming up to 60-65 ℃ of sustained reaction 1 hour; continue to be warming up to after the 85-90 ℃ of isothermal reaction 1 hour, moisture is removed in underpressure distillation under 70 ℃ boiling temperature, polymkeric substance is concentrated obtain product.
2. preparation method as claimed in claim 1 is characterized in that: said acrylic resin can be Butyl acrylate, vinylformic acid formicester, and optimum amount is 92-95% (weight).
3. preparation method as claimed in claim 1, it is characterized in that: said hydrophilizing agent is the monomer that has hydrophilic radical and strong polar group, as n-methylolacrylamide, hydroxyethyl CALCIUM ACRYLATE, hydroxyethyl methacrylate, hydroxypropyl (methyl) CALCIUM ACRYLATE and methacrylic acid etc.
4. preparation method as claimed in claim 1 is characterized in that: said initiator adopts azo-initiator, and as Diisopropyl azodicarboxylate, optimum amount is 1-2% (weight).
6. preparation method as claimed in claim 1 is characterized in that: the agent of said water-based chain extension-crosslinking is a polyvinyl alcohol.
7. preparation method as claimed in claim 1 is characterized in that: said emulsifying agent is a sodium lauryl sulphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97100555 CN1161377A (en) | 1997-01-31 | 1997-01-31 | Method for preparing leather repairing agent made of polyacrylates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97100555 CN1161377A (en) | 1997-01-31 | 1997-01-31 | Method for preparing leather repairing agent made of polyacrylates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1161377A true CN1161377A (en) | 1997-10-08 |
Family
ID=5165145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97100555 Pending CN1161377A (en) | 1997-01-31 | 1997-01-31 | Method for preparing leather repairing agent made of polyacrylates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1161377A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040431A1 (en) * | 2003-10-20 | 2005-05-06 | Basf Aktiengesellschaft | Method for coating leather with dispersed synthetic resin |
| CN1970795B (en) * | 2006-09-19 | 2010-05-12 | 山东联合化工股份有限公司 | Leather repairing paste and method for preparing same |
-
1997
- 1997-01-31 CN CN 97100555 patent/CN1161377A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040431A1 (en) * | 2003-10-20 | 2005-05-06 | Basf Aktiengesellschaft | Method for coating leather with dispersed synthetic resin |
| RU2370544C2 (en) * | 2003-10-20 | 2009-10-20 | Басф Акциенгезельшафт | Method to eliminate defects in skin grain patter layer with natural frain pattern and skin with eliminated grain pattern defects |
| CN1970795B (en) * | 2006-09-19 | 2010-05-12 | 山东联合化工股份有限公司 | Leather repairing paste and method for preparing same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |