CN101440151A - Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather and preparation thereof - Google Patents
Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather and preparation thereof Download PDFInfo
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- CN101440151A CN101440151A CNA2008102339753A CN200810233975A CN101440151A CN 101440151 A CN101440151 A CN 101440151A CN A2008102339753 A CNA2008102339753 A CN A2008102339753A CN 200810233975 A CN200810233975 A CN 200810233975A CN 101440151 A CN101440151 A CN 101440151A
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- polyacrylic acid
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Abstract
The invention discloses a wet-polyurethane grafted polyacrylic acid copolymer resin for embossed leather, and a preparation method thereof. The method comprises the following step of grafting polyacrylic acid onto a polymer chain of polyurethane (PU) during the synthesis of polyurethane (PU) resin, so as to obtain the polyurethane resin with a novel structure. The structural characteristics of polyacrylic acid determine the good plasticity of the resin, lower the heating-softening temperature of the resin, improve the embossing performance of the resin after turning into leather, and ensure that decorative patterns on the surface of leather are easier to shape, clearer, more prominent and better in stereoscopic sense. The wet-polyurethane grafted polyacrylic acid copolymer resin for embossed leather completely overcomes the defect that the prior common polyurethane resin is poor in embossing performance. Synthetic leather made from the wet-polyurethane grafted polyacrylic acid copolymer resin for embossed leather is easy to emboss, clear and prominent in decorative patterns and better in the stereoscopic sense of the decorative patterns.
Description
Technical field
The present invention relates to a kind of wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather, is a kind of sofa artificial leather, luggage leather, ball leather and sports play shoes leather Wet-type polyurethane embossing resin, also relates to its preparation method.
Background technology
Because the natural resources of corium product is limited, the price height can't satisfy the growing market requirement.And Synthetic Leather products material wide material sources, low price, good processability satisfies people's life seek fully.The Synthetic Leather product of especially high rerum natura extensively uses.At present, most popular is to be the main sofa artificial leather that processes, luggage leather, ball leather and sports play shoes leather etc. with the embossing.Defectives such as yet the chemical structure characteristic owing to urethane determines its existing elasticity preferably, and higher intensity is arranged again, rebounds easily after the embossing of urethane (PU) resin like this, and decorative pattern is difficult for typing, causes decorative pattern unintelligible, and plumpness is not enough.
Summary of the invention
The objective of the invention is to prepare a kind of wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather and preparation method thereof, exist the embossability defect of bad to solve common polyurethane resin.
A kind of wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather is characterized in that: the proportioning of its material component is:
Vulcabond;
Polyol compound;
Polyacrylic resin, consumption account for 0.5～1% of system gross weight;
Molecular weight is the small molecules dibasic alcohol chainextender of 62～200g/mol, and consumption accounts for 1～5% of system gross weight;
Catalyzer;
Auxiliary agent, consumption account for 0.05～0.08% of system gross weight;
Solvent;
Wherein, ratio 1:4～5 of polyol compound and the molar weight of the material of small molecules dibasic alcohol chainextender; The ratio of the molar weight of hydroxyl is in diisocyanate based and polyol compound, the dibasic alcohol chainextender: 1:1～1.05:1.The system gross weight comprises solvent.
Described wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate (MDI); Described polyol compound is meant one or both the mixing in polyester polyol, the polyether glycol; Described molecular weight is that the dibasic alcohol chainextender of 62～200g/mol is an ethylene glycol, 1,4-butyleneglycol, 1, one or both in the 6-hexylene glycol; Described catalyzer is organo-bismuth class catalyzer MB20, and consumption is 0.1 ‰ of polyol compound weight ~ 1 ‰; Described auxiliary agent is one or more the mixing in oxidation inhibitor, UV light absorber, weather-proof stablizer, the flow agent; Described solvent is water-soluble organic solvent, and consumption is 69%～71% of a system gross weight.
Described wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather is characterized in that: the dibasic alcohol chainextender is an ethylene glycol or/and 1, the 4-butyleneglycol, and two kinds of alcohol mix when using, and its molar ratio is 0.1:1～10:1; Described polyether glycol is a polytetramethylene ether diol; Solvent is N, dinethylformamide DMF.
Described a kind of wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather is characterized in that, according to the following steps preparation:
(2) after input polyester polyols alkylol cpd, oxidation inhibitor I-1010, solvent DMF fully stir evenly in reactor, vulcabond is joined again and carry out prepolymerization reaction in the reactor, solid content is 65%～75% during pre-polymerization, and viscosity controller is 20,000～40,000CPS/70-80 ℃;
(2) under the condition that catalyzer exists, continuation and vulcabond, small molecules dibasic alcohol chainextender react, add polyacrylic resin midway and participate in reaction, continuous increase along with system viscosity, progressively add required solvent DMF, final viscosity is controlled at 150,000～250,000CPS/25 ℃;
(3) reaction finishes an amount of terminator methyl alcohol of back adding etc., adds UV light absorber, weather-proof stablizer or flow agent at last again, to improve the shelf lives of resin;
Involved polyester polyol, vulcabond, small molecules dibasic alcohol chainextender, solvent etc. all require water ratio less than 500ppm in step (1) and (2);
Temperature of reaction in step (1) and (2) is controlled at 70～80 ℃.
The present invention is in urethane (PU) resin building-up process, to urethane (PU) macromolecular chain, finally obtains a kind of urethane resin of novel texture with polyacrylic acid grafted.Because polyacrylic constitutional features determines this resin to have good plasticity-, has reduced the softening temperature that is heated of resin, the embossability behind the raising resin finished leather is finalized the design break easily, and decorative pattern is more clear, fuller, stereoscopic sensation is stronger.
Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather of the present invention has solved existing common polyurethane resin fully and has existed the embossability defect of bad.The synthetic leather that uses Wet-type polyurethane grafting polyacrylic acid copolymerized resin of the present invention to make is easy to embossing, and decorative pattern is clear, full, stereoscopic sensation is strong.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with embodiment, further set forth the present invention.
Embodiment 1:
Material name weight (unit K g)
PET—1 200
PET—2 700
Ethylene glycol 110
4,4-diphenylmethanediisocyanate 545
Oxidation inhibitor I-1010 2.0
UV light absorber UV-328 1.0
Catalyzer 0.2
Polyacrylic acid 35
N, dinethylformamide 3720
PET-1 is the polyester polyol of molecular weight 4000, and raw materials used and prescription is hexanodioic acid 4000Kg, ethylene glycol 1300Kg, 1,4-butyleneglycol 900Kg, catalyzer TPT0.5Kg.
PET-2 is the polyester polyol of molecular weight 2000, and raw materials used and prescription is hexanodioic acid 3000Kg, ethylene glycol 200Kg, 1,4-butyleneglycol 1800Kg, catalyzer TPT0.4Kg.
Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather of the present invention is prepared according to the following steps:
1, the various polyol compounds of input, oxidation inhibitor I-1010, DMF stir after 10 minutes～20 minutes and drop into MDI in reactor, this moment, solid content should be controlled at 70%, NCO/OH is 0.92～0.98, the still temperature control is reacted more than 2 hours at 70 ℃～80 ℃, viscosity controller is 20,000～40,000cps/70-80 ℃.
2, adding DMF stirs after 10 minutes and drops into ethylene glycol (EG), stirs and drops into the MDI reaction in 20 minutes again, reacts to add catalyzer continuation reaction after 30 minutes again.This moment, the still temperature control was at 60～70 ℃.
3, add polyacrylic resin and drop into MDI and react midway, and, progressively add required solvent DMF along with the continuous increase of system viscosity.Final viscosity is controlled at 150,000～250,000 cps/25 ℃, adds UV light absorber UV-328.The still temperature control is between 70～80 ℃.
4, be cooled to and rush down material, metering packing below 60 ℃.
Embodiment 2:
Material name weight (unit K g)
PET—1 200
PET—2 700
1,4-butyleneglycol 160
4,4-diphenylmethanediisocyanate 545
Oxidation inhibitor I-1010 2.0
UV light absorber UV-328 1.0
Catalyzer 0.2
Polyacrylic acid 35
N, dinethylformamide 3830
PET-1 is the polyester polyol of molecular weight 4000, and raw materials used and prescription is hexanodioic acid 4000Kg, ethylene glycol 1300Kg, 1,4-butyleneglycol 900Kg, catalyzer TPT0.5Kg.
PET-2 is the polyester polyol of molecular weight 2000, and raw materials used and prescription is hexanodioic acid 3000Kg, ethylene glycol 200Kg, 1,4-butyleneglycol 1800Kg, catalyzer TPT0.4Kg.
Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather of the present invention is prepared according to the following steps:
1, the various polyol compounds of input, oxidation inhibitor I-1010, DMF stir after 10 minutes～20 minutes and drop into MDI in the reactor.This moment, solid content should be controlled at 70%, and NCO/OH is 0.92～0.98, and more than 2 hours, viscosity controller is 20,000～40,000cps/70-80 ℃ 70 ℃～80 ℃ reactions in the still temperature control.
2, add the DMF stirring and drop into 1 after 10 minutes, 4-butyleneglycol (BG) stirs and dropped into the MDI reaction in 20 minutes again, reacts to add catalyzer continuation reaction after 30 minutes again.This moment, the still temperature control was at 60～70 ℃.
3, add polyacrylic resin and drop into MDI and react midway, and, progressively add required solvent DMF along with the continuous increase of system viscosity.Final viscosity is controlled at 150,000～250,000 cps/25 ℃, adds UV light absorber UV-328.The still temperature control is between 70～80 ℃.
4, be cooled to and rush down material, metering packing below 60 ℃.
Verification the verifying results scheme 3:
In order to verify that wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather of the present invention has embossability preferably, the resin that above-mentioned embodiment is prepared is made synthetic leather by following prescription, concrete process hides prescription is as follows:
Resin 100
DMF 60
H
2O 2
B-90 4
S-91 2
Wood powder 15
Mill base is an amount of
After testing, the Wet-type polyurethane synthetic leather with the prescription of above-mentioned enforcement is made has good embossability, embossing easily, and also decorative pattern is clear, full, stereoscopic sensation is strong.
The so-called system of the present invention is meant whole reaction system, is exactly the total amount of all substances.That describes in above-mentioned embodiment and the specification sheets just illustrates principle of the present invention, and the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all belong to content of the present invention.
Claims (4)
1, a kind of wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather is characterized in that: the proportioning of its material component is:
Vulcabond;
Polyol compound;
Polyacrylic resin, consumption account for 0.5～1% of system gross weight;
Molecular weight is the small molecules dibasic alcohol chainextender of 62～200g/mol, and consumption accounts for 1～5% of system gross weight;
Catalyzer;
Auxiliary agent, consumption account for 0.05～0.08% of system gross weight;
Solvent;
Wherein, ratio 1:4～5 of polyol compound and the molar weight of the material of small molecules dibasic alcohol chainextender; The ratio of the molar weight of hydroxyl is in diisocyanate based and polyol compound, the dibasic alcohol chainextender: 1:1～1.05:1.The system gross weight comprises solvent.
2, wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather according to claim 1 is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate (MDI); Described polyol compound is meant one or both the mixing in polyester polyol, the polyether glycol; Described molecular weight is that the dibasic alcohol chainextender of 62～200g/mol is an ethylene glycol, 1,4-butyleneglycol, 1, one or both in the 6-hexylene glycol; Described catalyzer is organo-bismuth class catalyzer MB20, and consumption is 0.1 ‰ of polyol compound weight ~ 1 ‰; Described auxiliary agent is one or more the mixing in oxidation inhibitor, UV light absorber, weather-proof stablizer, the flow agent; Described solvent is water-soluble organic solvent, and consumption is 69%～71% of a system gross weight.
3, wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather according to claim 1 is characterized in that: the dibasic alcohol chainextender is an ethylene glycol or/and 1, the 4-butyleneglycol, and two kinds of alcohol mix when using, and its molar ratio is 0.1:1～10:1; Described polyether glycol is a polytetramethylene ether diol; Solvent is N, dinethylformamide DMF.
4, a kind of preparation a kind of wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather as claimed in claim 1 is characterized in that, according to the following steps preparation:
(1) after input polyester polyols alkylol cpd, oxidation inhibitor I-1010, solvent DMF fully stir evenly in reactor, vulcabond is joined again and carry out prepolymerization reaction in the reactor, solid content is 65%～75% during pre-polymerization, and viscosity controller is 20,000～40,000CPS/70-80 ℃;
(2) under the condition that catalyzer exists, continuation and vulcabond, small molecules dibasic alcohol chainextender react, add polyacrylic resin midway and participate in reaction, continuous increase along with system viscosity, progressively add required solvent DMF, final viscosity is controlled at 150,000～250,000CPS/25 ℃;
(3) reaction finishes an amount of terminator methyl alcohol of back adding etc., adds UV light absorber, weather-proof stablizer or flow agent at last again, to improve the shelf lives of resin;
Involved polyester polyol, vulcabond, small molecules dibasic alcohol chainextender, solvent etc. all require water ratio less than 500ppm in step (1) and (2);
Temperature of reaction in step (1) and (2) is controlled at 70～80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102339753A CN101440151B (en) | 2008-12-19 | 2008-12-19 | Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102339753A CN101440151B (en) | 2008-12-19 | 2008-12-19 | Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101440151A true CN101440151A (en) | 2009-05-27 |
| CN101440151B CN101440151B (en) | 2012-10-31 |
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| CN2008102339753A Active CN101440151B (en) | 2008-12-19 | 2008-12-19 | Wet-type polyurethane grafting polyacrylic acid copolymerized resin for embossed leather and preparation thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899783A (en) * | 2010-06-30 | 2010-12-01 | 安徽安利合成革股份有限公司 | Method for producing highly cold-resistant automobile gear sleeve leather |
| CN103467696A (en) * | 2013-08-16 | 2013-12-25 | 合肥安利聚氨酯新材料有限公司 | Preparation method of soft high-elasticity embossed sofa leather wet-method polyurethane resin |
| CN116377733A (en) * | 2022-12-14 | 2023-07-04 | 安徽安利材料科技股份有限公司 | Polyurethane synthetic leather and preparation method and application thereof |
-
2008
- 2008-12-19 CN CN2008102339753A patent/CN101440151B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899783A (en) * | 2010-06-30 | 2010-12-01 | 安徽安利合成革股份有限公司 | Method for producing highly cold-resistant automobile gear sleeve leather |
| CN103467696A (en) * | 2013-08-16 | 2013-12-25 | 合肥安利聚氨酯新材料有限公司 | Preparation method of soft high-elasticity embossed sofa leather wet-method polyurethane resin |
| CN103467696B (en) * | 2013-08-16 | 2016-07-06 | 合肥安利聚氨酯新材料有限公司 | A kind of preparation method of soft high-elasticity embossing sofa leather wet-method polyurethane resin |
| CN116377733A (en) * | 2022-12-14 | 2023-07-04 | 安徽安利材料科技股份有限公司 | Polyurethane synthetic leather and preparation method and application thereof |
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| CN101440151B (en) | 2012-10-31 |
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