CN103694402B - A kind of water-soluble colloidality polyacrylic ester filling resin for leather and preparation technology thereof - Google Patents
A kind of water-soluble colloidality polyacrylic ester filling resin for leather and preparation technology thereof Download PDFInfo
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- CN103694402B CN103694402B CN201310650268.5A CN201310650268A CN103694402B CN 103694402 B CN103694402 B CN 103694402B CN 201310650268 A CN201310650268 A CN 201310650268A CN 103694402 B CN103694402 B CN 103694402B
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- 239000010985 leather Substances 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 150000002148 esters Chemical class 0.000 title claims abstract description 28
- 238000005516 engineering process Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 58
- 239000003999 initiator Substances 0.000 claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012874 anionic emulsifier Substances 0.000 claims description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000007596 consolidation process Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 9
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000004160 Ammonium persulphate Substances 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention belongs to leather chemical industry field, provide a kind of water-soluble colloidality polyacrylic ester filling resin for leather and preparation technology thereof.It is characterized in that: by mass, filling resin for leather raw material comprises following component: reactive emulsifier 0.2 ~ 0.5%, initiator 0.1 ~ 0.3%, emulsifying agent 0.5 ~ 2%, acrylic ester monomer 15 ~ 25%, vinylformic acid 1 ~ 3%, and all the other are water.Water-sol filling resin for leather of the present invention, can have fabulous filling effect to the loose side position of leather, make the more plentiful consolidation of finished leather, not affect the Spraying technique again of leather.
Description
Technical field
The invention belongs to leather chemical industry field, be specifically related to a kind of water-soluble colloidality polyacrylic ester filling resin for leather and preparation technology thereof.
Background technology
The loose side of leather and grievous injury physical and mechanical properties of flaking, reduce grade and the utilization ratio of leather, become a difficult problem of China's tanning industry.Acrylic polymers has good weathering resistance, rub resistance, tint retention, and the penetration degree of the latex of this type of superpolymer on leather easily regulates.The hard soft degree of material, also by changing the proportioning free adjustment of monomer.Therefore, fill at leather and modify, usually adopt the multipolymer based on vinylformic acid.Simple Emulsion acrylic resin generally can not meet the requirement that leather is filled, and the acrylic resin overwhelming majority of therefore leather filling is at present all through modification to a certain degree.
Existing filling resin for leather is generally prepared by traditional emulsion polymerisation process, and product pellet size, between 100-300nm, for filling the loose side solving leather, shows as infiltration slow, is difficult to the specification of quality meeting leather filling.And hydrosol type leather filling resin, product pellet size is at below 100nm, and it can solve leather loose side problem effectively, makes finished leather plentiful, and has good flexibility and elasticity.There are two large shortcomings in existing water-sol resin syntheses processes:
1, the content of emulsifying agent is higher than 10%, and emulsifying agent is small-molecule substance normally, combines, can move during film forming by physical adsorption; The amount of emulsifying agent is too many, and leather is water-fast can be deteriorated; Because potting resin is filled for leather, emulsifying agent can affect leather filling properties too much and be coated with the clinging power of interlayer.
2, need assistant for emulsifying agent, assistant for emulsifying agent is organic solvent, and the use of organic solvent is unfavorable for environmental protection; Meanwhile, organic solvent can produce bad impact to leather.
As 02113740.4, denomination of invention is the patent of invention of " preparation method of hydrosol type leather filling resin ", discloses a kind of preparation method of hydrosol type leather filling resin, is by acrylic ester monomer 20 ~ 30%, tensio-active agent 0.2 ~ 2%, initiator 0.1 ~ 2%, amphiphilic solvent 5 ~ 30%, alkali 1 ~ 5%, molecular weight regulator 0 ~ 2%, all the other are water, polyreaction 1 ~ 4 hour at 60 ~ 90 DEG C, obtained hydrosol type leather filling resin.The amphiphilic solvent that this patent uses is organic solvent, is unfavorable for environmental protection, and can produces bad impact to leather.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of water-soluble colloidality polyacrylic ester filling resin for leather and preparation technology thereof.Water-sol filling resin for leather of the present invention, can have fabulous filling effect to the loose side position of leather, make the more plentiful consolidation of finished leather, not affect the Spraying technique again of leather.Preparation technology of the present invention is applicable to suitability for industrialized production, and batch product is stable.
For achieving the above object, the present invention adopts following technical scheme:
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, it is characterized in that: by mass, raw material comprises following component:
Reactive emulsifier 0.2 ~ 0.5%
Initiator 0.1 ~ 0.3%
Emulsifying agent 0.5 ~ 2%
Acrylic ester monomer 15 ~ 25%
Vinylformic acid 1 ~ 3%
All the other are water.
Reactive emulsifier is combined on particle surface in the mode of covalent linkage, namely emulsifier molecules and macromolecular chain are with covalent bonds, decapacitation solves outside the water tolerance problem of leather well, and also will the recycle of waste water is more prone to, the pollution of environment reduces further; Especially obtained without free emulsifying agent latex, the formation of foam can be reduced when transporting thus make it transport to become convenient.
Reactive emulsifier of the present invention is 2-acrylamide-2-methyl propane sulfonic sodium, allyloxy hydroxyl sulfoacid sodium, vinyl carbinol b-oxide sodium sulfate or polymerizable type Phosphate Anionic Surfactants.
Preferably, described reactive emulsifier is 2-acrylamide-2-methyl propane sulfonic sodium, while improving water tolerance, reducing the amount of small-molecular emulsifier, effectively can improve the perviousness of emulsion.
Emulsifying agent of the present invention is that 1.5 ~ 2.5:1 is composite in mass ratio for anionic emulsifier and nonionic emulsifying agent.
Preferably, any one or two or more mixtures in described anionic emulsifier sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate.The granularity of the present latex particulate generated is less, and latex stability is good, is not easy to produce cohesion block in polymerization process, improves stability of emulsion polymerization.
Preferably, described nonionic emulsifying agent is any one or two or more mixture in SA-9, DIPONILA-4056, EmulsogenLCN407, paregal O.Good to electrolytical chemical stability, improve emulsion storage stability.
Acrylic ester monomer of the present invention is any one or two or more mixture in methyl methacrylate, vinylformic acid, methyl acrylate, butyl acrylate, ethyl propenoate, Isooctyl acrylate monomer.
The solid content of water-soluble polyacrylate filling resin for leather of the present invention is 21 ~ 23%, PH is 7.5 ~ 8.5, viscosity is < 15m.pa.s.
The preparation technology of the present invention's water-soluble colloidality polyacrylic ester filling resin for leather, comprises the following steps:
A, by soluble in water for the emulsifying agent of formula ratio, after being warmed up to 70 ~ 75 DEG C, adds the initiator solution of the acrylate monomer of 2 ~ 5% formula ratios, vinylformic acid and reactive emulsifier and 25 ~ 50% formula ratios;
B reacting by heating 10 ~ 20min, temperature of reaction rises to 80 ~ 85 DEG C, the acrylate monomer of remaining formula ratio, vinylformic acid, reactive emulsifier and initiator is evenly added drop-wise in reactor and reacts in 1.5 ~ 2h;
Insulation reaction 1 ~ 1.5h is continued again after C dropwises; Be cooled to 50 DEG C again, add alkali lye, make its Ph be 7.5 ~ 8.5, filter and get final product.
Beneficial effect of the present invention is:
1, water-sol filling resin for leather raw material of the present invention adopts reactive emulsifier, and emulsifier content only has 0.5 ~ 2%, is not containing the environmental protection product of APEO, organic solvent.Decapacitation solves outside the water tolerance problem of leather well, and also will the recycle of waste water is more prone to, the pollution of environment reduces further; There is extremely strong perviousness and clinging power, be a kind of desirable wholegrain face potting resin, obviously can reduce the loose side of leather, little on the impact of finished leather body bone; Especially obtained without free emulsifying agent latex, the formation of foam can be reduced when transporting thus make it transport to become convenient; Reaction emulsifier also helps emulsion particle with anionic charge and forms double electrical layers, thus improves stability of emulsion polymerization and stability in storage.
2, the present invention selects 2-acrylamide-2-methyl propane sulfonic sodium as reactive emulsifier, while improving water tolerance, reducing the amount of small-molecular emulsifier, effectively can also improve the perviousness of emulsion, penetration time was reduced to 7 seconds from original 20 seconds, makes leather hand feeling smooth, soft, plentiful.
3, by anionic emulsifier and nonionic emulsifying agent, 1.5 ~ 2.5:1 is composite in mass ratio in the present invention, and the granularity of the present latex particulate of generation is less, and latex stability is good, is not easy to produce cohesion block in polymerization process, improves the polymerization stability of emulsion further.
4, prior art generally adopt 10% ~ 15% emulsifying agent, monomer mixture and initiator solution as seed emulsion, the emulsion particle quantity of generation is few, particle diameter is greater than 90nm.Preparation technology of the present invention is by the monomer mixture acrylate monomer of whole emulsifying agent, 2 ~ 5% formula ratios and reactive emulsifier, and 25 ~ 50% formula ratio initiator solution be used for seed emulsion, the particle diameter generating emulsion particle is 40 ~ 60nm, emulsion particle is many and little, and the filling effect of obtained potting resin is good.
Embodiment
Below in conjunction with embodiment, essentiality content of the present invention is described in further detail.
Embodiment 1
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, raw material comprises following component:
Vinyl carbinol b-oxide sodium sulfate 0.2%
Initiator 0.1%
Sodium laurylsulfonate 0.3%
SA-90.2%
Methyl methacrylate 15%
Vinylformic acid 1%
All the other are water.
Initiator of the present invention is water miscible thermal initiator:
Persulphate: ammonium persulphate, Sodium Persulfate, Potassium Persulphate;
Redox initiator: Potassium Persulphate and sodium bisulfite, ammonium persulphate and vat powder, tert-butyl peroxide and pillbox white powder etc.;
Or help reductive agent metal-salt: ferrous sulfate, cuprous sulfate etc.
Embodiment 2
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, raw material comprises following component:
2-acrylamide-2-methyl propane sulfonic sodium 0.5%
Initiator 0.3%
Sodium lauryl sulphate 0.75%
DIPONILA-40560.3%
Butyl acrylate 25%
Vinylformic acid 3%
All the other are water.
Embodiment 3
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, raw material comprises following component:
Allyloxy hydroxyl sulfoacid sodium 0.3%
Initiator 0.2%
Sodium dodecylbenzene sulfonate 1.2%
EmulsogenLCN4070.8%
Methyl acrylate 20%
Vinylformic acid 1%
All the other are water.
The solid content of water-soluble polyacrylate filling resin for leather is 21%, PH is 7.5, viscosity is < 15m.pa.s.
Embodiment 4
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, raw material comprises following component:
Allyloxy hydroxyl sulfoacid sodium 0.4%
Initiator 0.15%
Sodium dodecylbenzene sulfonate 1.0%
EmulsogenLCN4070.8%
Butyl acrylate 16%
Methyl acrylate 5%
Vinylformic acid 1%
All the other are water.
The solid content of water-soluble polyacrylate filling resin for leather is 23%, PH is 8.5, viscosity is < 15m.Pa.s.
Embodiment 5
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, raw material comprises following component:
Polymerizable type Phosphate Anionic Surfactants 0.25%
Initiator 0.18%
Sodium dodecylbenzene sulfonate 0.4%
Sodium lauryl sulphate 0.4%
Paregal O 0.4%
Ethyl propenoate 20%
Vinylformic acid 1.5%
All the other are water.
The solid content of water-soluble polyacrylate filling resin for leather is 22%, PH is 7.6, viscosity is < 15m.Pa.s.
Embodiment 6
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, raw material comprises following component:
Polymerizable type Phosphate Anionic Surfactants 0.26%
Initiator 0.25%
Sodium dodecylbenzene sulfonate 0.5%
Sodium lauryl sulphate 0.3%
Paregal O 0.3%
SA-90.2%
Isooctyl acrylate monomer 21%
Vinylformic acid 1%
All the other are water.
The solid content of water-soluble polyacrylate filling resin for leather is 22%, PH is 8.0, viscosity is < 15m.Pa.s.
Embodiment 7
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, feed composition is as follows:
2-acrylamide-2-methyl propane sulfonic sodium 0.45%
Initiator 0.27%
Sodium lauryl sulphate 1.0%
SA-90.6
Methyl methacrylate 5%
Ethyl propenoate 19%
Vinylformic acid 2%
All the other are water.
The solid content of water-soluble polyacrylate filling resin for leather is 21%, PH is 8.3, viscosity is < 15m.Pa.s.
Embodiment 8
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, feed composition is as follows:
2-acrylamide-2-methyl propane sulfonic sodium 0.36%
Initiator 0.28%
Sodium lauryl sulphate 1.0%
EmulsogenLCN0.4%
Methyl acrylate 10%
Ethyl propenoate 10%
Vinylformic acid 1%
All the other are water.
The solid content of water-soluble polyacrylate filling resin for leather is 22%, PH is 7.5, viscosity is 15m.Pa.s.
Embodiment 9
A kind of water-soluble colloidality polyacrylic ester filling resin for leather, by mass, feed composition is as follows:
2-acrylamide-2-methyl propane sulfonic sodium 0.33%
Initiator 0.22%
Sodium dodecylbenzene sulfonate 1.2%
EmulsogenLCN0.5%
Butyl acrylate 7%
Ethyl propenoate 15%
Vinylformic acid 2%
All the other are water.
The solid content of water-soluble polyacrylate filling resin for leather is 25%, PH is 7.8, viscosity is < 15m.Pa.s.
Embodiment 10
The preparation technology of the present invention's water-soluble colloidality polyacrylic ester filling resin for leather, comprises the following steps:
A, by soluble in water for the emulsifying agent of formula ratio, after being warmed up to 70 DEG C, adds the initiator solution of the acrylate monomer of 2% formula ratio, vinylformic acid and reactive emulsifier and 25% formula ratio;
B reacting by heating 10min, temperature of reaction rises to 85 DEG C, the acrylate monomer of remaining formula ratio, vinylformic acid, reactive emulsifier and initiator is evenly added drop-wise in reactor and reacts in 2h;
Insulation reaction 1h is continued again after C dropwises; Be cooled to 50 DEG C again, add alkali lye, make its Ph be 8.5, filter and get final product.
Embodiment 11
The preparation technology of the present invention's water-soluble colloidality polyacrylic ester filling resin for leather, comprises the following steps:
A, by soluble in water for the emulsifying agent of formula ratio, after being warmed up to 75 DEG C, adds the initiator solution of the acrylate monomer of 5% formula ratio, vinylformic acid and reactive emulsifier and 50% formula ratio;
B reacting by heating 20min, temperature of reaction rises to 80 DEG C, the acrylate monomer of remaining formula ratio, vinylformic acid, reactive emulsifier and initiator is evenly added drop-wise in reactor and reacts in 1.5h;
Insulation reaction 1.5h is continued again after C dropwises; Be cooled to 50 DEG C again, add alkali lye, make its Ph be 7.5, filter and get final product.
Embodiment 12
The preparation technology of the present invention's water-soluble colloidality polyacrylic ester filling resin for leather, comprises the following steps:
A, by soluble in water for the emulsifying agent of formula ratio, after being warmed up to 72 DEG C, adds the initiator solution of the acrylate monomer of 3% formula ratio, vinylformic acid and reactive emulsifier and 30%;
B reacting by heating 15min, temperature of reaction rises to 82 DEG C, the acrylate monomer of remaining formula ratio, vinylformic acid, reactive emulsifier and initiator is evenly added drop-wise in reactor and reacts in 1.6h;
Insulation reaction 1.3h is continued again after C dropwises; Be cooled to 50 DEG C again, add alkali lye, make its Ph be 8.0, filter and get final product.
Embodiment 13
The preparation technology of the present invention's water-soluble colloidality polyacrylic ester filling resin for leather, comprises the following steps:
A, by soluble in water for the emulsifying agent of formula ratio, after being warmed up to 73 DEG C, adds the initiator solution of the acrylate monomer of 4% formula ratio, vinylformic acid and reactive emulsifier and 40%;
B reacting by heating 18min, temperature of reaction rises to 83 DEG C, the acrylate monomer of remaining formula ratio, vinylformic acid, reactive emulsifier and initiator is evenly added drop-wise in reactor and reacts in 1.8h;
Insulation reaction 1.2h is continued again after C dropwises; Be cooled to 50 DEG C again, add ammoniacal liquor, make its Ph be 7.6, filter and get final product.
Embodiment 14
The preparation technology of the present invention's water-soluble colloidality polyacrylic ester filling resin for leather, comprises the following steps:
A, by soluble in water for the emulsifying agent of formula ratio, after being warmed up to 74 DEG C, adds the initiator solution of the acrylate monomer of 3.5% formula ratio, vinylformic acid and reactive emulsifier and 45%;
B reacting by heating 16min, temperature of reaction rises to 84 DEG C, the acrylate monomer of remaining formula ratio, vinylformic acid, reactive emulsifier and initiator is evenly added drop-wise in reactor and reacts in 1.7h;
Insulation reaction 1.4h is continued again after C dropwises; Be cooled to 50 DEG C again, add ammoniacal liquor, make its Ph be 8.2, filter and get final product.
Embodiment 15
In 500ml four-hole boiling flask, drop into deionized water 200 grams, emulsifying agent 4 grams (wherein sodium lauryl sulphate 2.5 grams, SA-91.5 gram), stirs and is warming up to 75 DEG C.Esters of acrylic acid 75 grams (wherein methyl methacrylate 10 grams, ethyl propenoate 62 grams and 3 grams, vinylformic acid) and 2 grams, 2-acrylamide-2-methyl propane sulfonic sodium are mixed and is made into monomer mixture.0.40 gram of ammonium persulphate is dissolved in 40 grams of deionized waters and is made into initiator.1.5 grams of monomer mixtures, 15 grams of initiators are dropped into together in four-hole boiling flask, reacting by heating 15 minutes again, treat that micro emulsion blue light appears in emulsion, then be warming up to 82 DEG C, residual monomer mixture and initiator are evenly added drop-wise in four-hole boiling flask by 2h; Insulation 1.5h is continued again after dropwising; Cool to 50 DEG C, add 3 grams of ammoniacal liquor, regulate pH to be 8.0, solid content 21%, filter.
Embodiment 16
In 500ml four-hole boiling flask, drop into deionized water 200 grams, emulsifying agent 3 grams (wherein sodium lauryl sulphate 2 grams, EmulsogenLCN4071 gram), stirs and is warming up to 75 DEG C.Esters of acrylic acid 75 grams (wherein methyl acrylate 10 grams, ethyl propenoate 62 grams and 3 grams, vinylformic acid) and 3 grams, 2-acrylamide-2-methyl propane sulfonic sodium are mixed and is made into monomer mixture.0.40 gram of Potassium Persulphate is dissolved in 40 grams of deionized waters and is made into initiator.1.5 grams of monomer mixtures, 15 grams of initiators are dropped into together in four-hole boiling flask, reacting by heating 15 minutes again, treat that micro emulsion blue light appears in emulsion, then be warming up to 82 DEG C, residual monomer mixture and initiator are evenly added drop-wise in four-hole boiling flask by 2h; Insulation 1.5h is continued again after dropwising; Cool to 50 DEG C, add 3 grams of ammoniacal liquor, regulate pH to be 8.5, solid content 23%, filter.
Embodiment 17
In 500ml four-hole boiling flask, drop into deionized water 200 grams, emulsifying agent 4 grams (wherein Sodium dodecylbenzene sulfonate 2.5 grams, EmulsogenLCN4071.5 gram), stirs and is warming up to 75 DEG C.Esters of acrylic acid 75 grams (wherein butyl acrylate 40 grams, ethyl propenoate 32 grams and 3 grams, vinylformic acid) and 2 grams, 2-acrylamide-2-methyl propane sulfonic sodium are mixed and is made into monomer mixture.0.40 gram of ammonium persulphate is dissolved in 40 grams of deionized waters and is made into initiator.1.5 grams of monomer mixtures, 15 grams of initiators are dropped into together in four-hole boiling flask, reacting by heating 15 minutes again, treat that micro emulsion blue light appears in emulsion, then be warming up to 82 DEG C, residual monomer mixture and initiator are evenly added drop-wise in four-hole boiling flask by 2h; Insulation 1.5h is continued again after dropwising; Cool to 50 DEG C, add 3 grams of ammoniacal liquor, regulate pH to be 7.5, solid content 22%, filter.
Claims (6)
1. a water-soluble colloidality polyacrylic ester filling resin for leather, it is characterized in that: by mass, raw material comprises following component:
Reactive emulsifier 0.2 ~ 0.5%
Initiator 0.1 ~ 0.3%
Emulsifying agent 0.5 ~ 2%
Acrylic ester monomer 15 ~ 25%
Vinylformic acid 1 ~ 3%
All the other are water;
Described reactive emulsifier is 2-acrylamide-2-methyl propane sulfonic sodium.
2. one according to claim 1 water-soluble colloidality polyacrylic ester filling resin for leather, is characterized in that: described emulsifying agent is that 1.5 ~ 2.5:1 is composite in mass ratio for anionic emulsifier and nonionic emulsifying agent.
3. one according to claim 2 water-soluble colloidality polyacrylic ester filling resin for leather, is characterized in that: described anionic emulsifier is any one or two or more mixture in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate.
4. one according to claim 1 water-soluble colloidality polyacrylic ester filling resin for leather, is characterized in that: described acrylic ester monomer is any one or two or more mixture in methyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, Isooctyl acrylate monomer.
5. one according to claim 1 water-soluble colloidality polyacrylic ester filling resin for leather, is characterized in that: the solid content of described water-soluble polyacrylate filling resin for leather is 21 ~ 23%, pH is 7.5 ~ 8.5, viscosity is < 15mPas.
6. the preparation technology of a kind of water-soluble colloidality polyacrylic ester filling resin for leather according to claim 1, is characterized in that: comprise the following steps:
A, by soluble in water for the emulsifying agent of formula ratio, after being warmed up to 70 ~ 75 DEG C, adds the mixture of the acrylate monomer of 2 ~ 5% formula ratios, vinylformic acid and reactive emulsifier and the initiator solution of 25 ~ 50% formula ratios;
B reacting by heating 10 ~ 20min, temperature of reaction rises to 80 ~ 85 DEG C, the acrylate monomer of remaining formula ratio, vinylformic acid, reactive emulsifier and initiator is evenly added drop-wise in reactor and reacts in 1.5 ~ 2h;
After C dropwises, continue insulation reaction 1 ~ 1.5h; Be cooled to 50 DEG C again, add alkali lye, make its pH be 7.5 ~ 8.5, filter and obtain water-soluble colloidality polyacrylic ester filling resin for leather.
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| CN115960300B (en) * | 2022-12-29 | 2024-03-19 | 广东银洋环保新材料有限公司 | Acrylic emulsion for leather treatment and preparation method thereof |
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Denomination of invention: Water soluble polyacrylate leather filling resin and its preparation process Effective date of registration: 20220225 Granted publication date: 20160120 Pledgee: Industrial Bank Limited by Share Ltd. Chengdu branch Pledgor: DOWELL TECHNOLOGY Co.,Ltd. Registration number: Y2022510000047 |
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