CN104928943A - Preparation method of acrylate modified waterborne polyurethane emulsion for synthetic leather - Google Patents
Preparation method of acrylate modified waterborne polyurethane emulsion for synthetic leather Download PDFInfo
- Publication number
- CN104928943A CN104928943A CN201510339567.6A CN201510339567A CN104928943A CN 104928943 A CN104928943 A CN 104928943A CN 201510339567 A CN201510339567 A CN 201510339567A CN 104928943 A CN104928943 A CN 104928943A
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- CN
- China
- Prior art keywords
- preparation
- polyurethane emulsion
- acrylic ester
- ester modified
- synthetic leather
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 239000000839 emulsion Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002649 leather substitute Substances 0.000 title claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 9
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 acrylic ester Chemical class 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 5
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004049 embossing Methods 0.000 abstract description 3
- 239000004970 Chain extender Substances 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of acrylate modified waterborne polyurethane emulsion for synthetic leather, which is characterized in that active double bonds are introduced into acrylate modified waterborne polyurethane with a main chain, polybutadiene diol is used as a chain extender, the active double bonds are introduced into the main chain of polyurethane molecules, and then acrylate monomers are used for connecting the main chains of the polyurethane together through double bond polymerization, so that the acrylate modified waterborne polyurethane emulsion is synthesized. The preparation method of the invention has simple process, easy realization and good process implementation. The synthetic leather prepared by the method has soft hand feeling, good cold resistance and water resistance and excellent embossing effect, and has wide application prospect in the synthetic leather industry.
Description
Technical field
The present invention relates to synthetic leather field of material technology, particularly relate to a kind of preparation method of use for synthetic leather acrylic ester modified water-soluble polyurethane emulsion.
Background technology
Aqueous polyurethane has the ABRASION RESISTANCE of higher TENSILE STRENGTH and impact strength and excellence, but aqueous polyurethane has many hydrophilic radicals, thus poor water resistance, and cost is high.And have using acrylate as the coating of base-material and protect light, protect the advantages such as look, weather-proof, strong adhesion, but there is the glutinous shortcoming such as cold short of poor solvent resistance, heat simultaneously.Aqueous polyurethane and polyacrylate are having certain complementarity in nature, can play comprehensive advantage by compound.
But, aqueous polyurethane acrylate modified at present mainly with the water-based double bond blocked polyurethane of synthesis for seed emulsion emulsion acrylic ester monomer, and then by initator initiating methacrylates monomer, prepare modified product.In the water-based double bond blocked polyurethane of this method synthesis, the specific activity of double bond is poor, reacts wayward.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, a kind of preparation method of use for synthetic leather acrylic ester modified water-soluble polyurethane emulsion is provided, the synthetic leather obtained is soft, cold resistance and water-tolerant, embossing effects be excellent.
For achieving the above object, the present invention is achieved by the following technical solutions:
A preparation method for use for synthetic leather acrylic ester modified water-soluble polyurethane emulsion, described preparation method comprises the following steps:
(1) by the vulcabond of 2 ~ 3mol, the polybutadiene dihydroxylic alcohols of 1 ~ 2mol, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 3 ~ 5h, obtains base polyurethane prepolymer for use as;
(2) by the neopentyl glycol of 0.5 ~ 1.2mol and 2 ~ 5mol acrylic monomers, add in the reactant liquor that (1) obtain, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 5 ~ 8h, obtains base polyurethane prepolymer for use as;
(3) reactant liquor that (2) obtain is down to room temperature, adds pH value regulator and neutralize, add deionized water simultaneously and carry out emulsification, obtain aqueous polyurethane emulsion;
(4) joined by the initator of 0.5 ~ 1mol in the emulsion that (3) obtain, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 5 ~ 8h, can obtain acrylic ester modified water-soluble polyurethane emulsion.
Preferably, described vulcabond is any one in 2,6-toluene di-isocyanate(TDI), isophorone diisocyanate, '-diphenylmethane diisocyanate.
Preferably, described acrylate monomer is any one in hydroxyethyl methylacrylate, n-butyl acrylate, isobutyl acrylate.
Preferably, described pH value regulator is NaOH, NaCO
3, any one in ammoniacal liquor.
Beneficial effect of the present invention:
Compared with prior art, selected the polybutadiene dihydroxylic alcohols with double bond to form bridge as raw material in the present invention's synthesis, this raw material can react with acrylic monomers again with isocyanate groups reaction, reaches the object of polyacrylate modified polyurethane.Present invention process is simple, easily realizes, has good process implementing.Adopt that the synthetic leather prepared of the present invention is soft, cold resistance and water-tolerant, embossing effects be excellent, have a wide range of applications in synthetic leather industry.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
A preparation method for use for synthetic leather acrylic ester modified water-soluble polyurethane emulsion, described preparation method comprises the following steps:
(1) by the vulcabond of 2 ~ 3mol, the polybutadiene dihydroxylic alcohols of 1 ~ 2mol, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 3 ~ 5h, obtains base polyurethane prepolymer for use as;
(2) by the neopentyl glycol of 0.5 ~ 1.2mol and 2 ~ 5mol acrylic monomers, add in the reactant liquor that (1) obtain, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 5 ~ 8h, obtains base polyurethane prepolymer for use as;
(3) reactant liquor that (2) obtain is down to room temperature, adds pH value regulator and neutralize, add deionized water simultaneously and carry out emulsification, obtain aqueous polyurethane emulsion;
(4) joined by the initator of 0.5 ~ 1mol in the emulsion that (3) obtain, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 5 ~ 8h, can obtain acrylic ester modified water-soluble polyurethane emulsion.
Wherein, described vulcabond is any one in 2,6-toluene di-isocyanate(TDI), isophorone diisocyanate, '-diphenylmethane diisocyanate.Described acrylate monomer is any one in hydroxyethyl methylacrylate, n-butyl acrylate, isobutyl acrylate.Described pH value regulator is NaOH, NaCO
3, any one in ammoniacal liquor.
Embodiment 1
The preparation process of acrylic ester modified water-soluble polyurethane emulsion is as follows:
(1) by the isophorone diisocyanate of 3mol, the polybutadiene dihydroxylic alcohols of 2mol, under the temperature at 100 DEG C and the condition in argon shield, reaction 3 ~ 5h, obtains base polyurethane prepolymer for use as;
(2) by the neopentyl glycol of 1.2mol and 5mol n-butyl acrylate, add in the reactant liquor that (1) obtain, under the temperature at 100 DEG C and the condition in argon shield, reaction 8h, obtains base polyurethane prepolymer for use as;
(3) reactant liquor that (2) obtain is down to room temperature, adds NaCO
3neutralize, add deionized water simultaneously and carry out emulsification, obtain aqueous polyurethane emulsion;
(4) joined by the initator of 1mol in the emulsion that (3) obtain, under the temperature at 100 DEG C and the condition in argon shield, reaction 8h, can obtain acrylic ester modified water-soluble polyurethane emulsion.
Embodiment 2
The preparation process of acrylic ester modified water-soluble polyurethane emulsion is as follows:
(1) by 2, the 6-toluene di-isocyanate(TDI)s of 2mol, the polybutadiene dihydroxylic alcohols of 1mol, under the temperature at 70 DEG C and the condition in argon shield, reaction 3h, obtains base polyurethane prepolymer for use as;
(2) by the neopentyl glycol of 0.5mol and 2mol hydroxyethyl methylacrylate, add in the reactant liquor that (1) obtain, under the temperature at 70 DEG C and the condition in argon shield, reaction 5h, obtains base polyurethane prepolymer for use as;
(3) reactant liquor that (2) obtain is down to room temperature, adds NaOH and neutralize, add deionized water simultaneously and carry out emulsification, obtain aqueous polyurethane emulsion;
(4) joined by the initator of 0.5mol in the emulsion that (3) obtain, under the temperature at 70 DEG C and the condition in argon shield, reaction 5h, can obtain acrylic ester modified water-soluble polyurethane emulsion.
Embodiment 3
The preparation process of acrylic ester modified water-soluble polyurethane emulsion is as follows:
(1) by the '-diphenylmethane diisocyanate of 2.5mol, the polybutadiene dihydroxylic alcohols of 1.5mol, under the temperature at 80 DEG C and the condition in argon shield, reaction 4h, obtains base polyurethane prepolymer for use as;
(2) by the neopentyl glycol of 0.8mol and 4mol isobutyl acrylate, add in the reactant liquor that (1) obtain, under the temperature at 80 DEG C and the condition in argon shield, reaction 7h, obtains base polyurethane prepolymer for use as;
(3) reactant liquor that (2) obtain is down to room temperature, adds ammoniacal liquor and neutralize, add deionized water simultaneously and carry out emulsification, obtain aqueous polyurethane emulsion;
(4) joined by the initator of 0.7mol in the emulsion that (3) obtain, under the temperature at 70 DEG C and the condition in argon shield, reaction 6h, can obtain acrylic ester modified water-soluble polyurethane emulsion.
Embodiment 4
The preparation process of acrylic ester modified water-soluble polyurethane emulsion is as follows:
(1) by 2, the 6-toluene di-isocyanate(TDI)s of 3mol, the polybutadiene dihydroxylic alcohols of 2mol, under the temperature at 100 DEG C and the condition in argon shield, reaction 4h, obtains base polyurethane prepolymer for use as;
(2) by the neopentyl glycol of 0.5mol and 3mol hydroxyethyl methylacrylate, add in the reactant liquor that (1) obtain, under the temperature at 75 DEG C and the condition in argon shield, reaction 7h, obtains base polyurethane prepolymer for use as;
(3) reactant liquor that (2) obtain is down to room temperature, adds NaOH and neutralize, add deionized water simultaneously and carry out emulsification, obtain aqueous polyurethane emulsion;
(4) joined by the initator of 0.5mol in the emulsion that (3) obtain, under the temperature at 100 DEG C and the condition in argon shield, reaction 8h, can obtain acrylic ester modified water-soluble polyurethane emulsion.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (4)
1. a preparation method for use for synthetic leather acrylic ester modified water-soluble polyurethane emulsion, is characterized in that: described preparation method comprises the following steps:
(1) by the vulcabond of 2 ~ 3mol, the polybutadiene dihydroxylic alcohols of 1 ~ 2mol, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 3 ~ 5h, obtains base polyurethane prepolymer for use as;
(2) by the neopentyl glycol of 0.5 ~ 1.2mol and 2 ~ 5mol acrylic monomers, add in the reactant liquor that (1) obtain, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 5 ~ 8h, obtains base polyurethane prepolymer for use as;
(3) reactant liquor that (2) obtain is down to room temperature, adds pH value regulator and neutralize, add deionized water simultaneously and carry out emulsification, obtain aqueous polyurethane emulsion;
(4) joined by the initator of 0.5 ~ 1mol in the emulsion that (3) obtain, under the temperature at 70 ~ 100 DEG C and the condition in argon shield, reaction 5 ~ 8h, can obtain acrylic ester modified water-soluble polyurethane emulsion.
2. the preparation method of acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that: described vulcabond is any one in 2,6-toluene di-isocyanate(TDI), isophorone diisocyanate, '-diphenylmethane diisocyanate.
3. the preparation method of acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that: described acrylate monomer is any one in hydroxyethyl methylacrylate, n-butyl acrylate, isobutyl acrylate.
4. the preparation method of acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that: described pH value regulator is NaOH, NaCO
3, any one in ammoniacal liquor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510339567.6A CN104928943A (en) | 2015-06-18 | 2015-06-18 | Preparation method of acrylate modified waterborne polyurethane emulsion for synthetic leather |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510339567.6A CN104928943A (en) | 2015-06-18 | 2015-06-18 | Preparation method of acrylate modified waterborne polyurethane emulsion for synthetic leather |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192409A (en) * | 2016-07-29 | 2016-12-07 | 丹东优耐特纺织品有限公司 | Water writing cloth coating adhesive and processing method |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN110128936A (en) * | 2019-05-28 | 2019-08-16 | 朱建余 | A kind of use for synthetic leather surface treating agent and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399348A (en) * | 2011-10-18 | 2012-04-04 | 辽宁恒星精细化工有限公司 | Polyacrylate-modified polyurethane aqueous coating emulsion with high water pressure resistance and preparation method thereof |
-
2015
- 2015-06-18 CN CN201510339567.6A patent/CN104928943A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399348A (en) * | 2011-10-18 | 2012-04-04 | 辽宁恒星精细化工有限公司 | Polyacrylate-modified polyurethane aqueous coating emulsion with high water pressure resistance and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192409A (en) * | 2016-07-29 | 2016-12-07 | 丹东优耐特纺织品有限公司 | Water writing cloth coating adhesive and processing method |
| CN106192409B (en) * | 2016-07-29 | 2018-04-17 | 丹东优耐特纺织品有限公司 | Water writing cloth coating adhesive and processing method |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN110128936A (en) * | 2019-05-28 | 2019-08-16 | 朱建余 | A kind of use for synthetic leather surface treating agent and preparation method thereof |
| CN110128936B (en) * | 2019-05-28 | 2021-07-16 | 江苏多森新材料科技有限公司 | Surface treating agent for synthetic leather and preparation method thereof |
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