CN102329409A - Synthesis process for ultralow-density polyurethane sole stoste - Google Patents
Synthesis process for ultralow-density polyurethane sole stoste Download PDFInfo
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- CN102329409A CN102329409A CN 201110242647 CN201110242647A CN102329409A CN 102329409 A CN102329409 A CN 102329409A CN 201110242647 CN201110242647 CN 201110242647 CN 201110242647 A CN201110242647 A CN 201110242647A CN 102329409 A CN102329409 A CN 102329409A
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- Prior art keywords
- density polyurethane
- polyurethane sole
- polyester polyol
- composite catalyst
- stoste
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Abstract
The invention discloses a synthesis process for ultralow-density polyurethane sole stoste. The synthesis process comprises the steps of: subjecting dicarboxylic acid and polyatomic alcohol to polyesterification reaction under the action of a composite catalyst to obtain polyester polyol, wherein the composite catalyst comprises acetate, triethylene diamine and stannous octoate/silicon catalysts; mixing the obtained polyester polyol with a foam stabilizer, grafting polyester and silicone oil to obtain a component A; and pre-polymerizing the obtained polyester polyol with isocyanate and polyether polyol to obtain a component B. The synthesis process disclosed by the invention has the advantages of obvious energy-saving and emission reduction effect and high raw material utilization ratio. The ultralow-density polyurethane sole stoste prepared with the synthesis process has the advantages of lighter weight, wear abrasion, folding resistance, oil resistance, chemical resistance and the like. The traditional low-density polyurethane sole stoste has the sole molding density of 0.32-0.38, and the molding density of the ultralow-density polyurethane sole stoste in the invention is reduced to 0.26-0.30, so that the cost is greatly reduced and the economic benefits are increased.
Description
Technical field
The present invention relates to a kind of Chemicals synthesis technique, specifically be meant ultra-low density polyurethane sole stoste synthesis technique.
Background technology
The Along with people's growth in the living standard; People are also increasingly high to the footwear technical requirement; Because the low-density polyurethane sole has advantages such as light weight, wear-resisting, folding, oil resistant, chemicals-resistant, people improve low-density polyurethane sole stoste demand day by day.But it is to adopt high-density technology mostly that existing low-density polyurethane sole stoste is produced, and its flow process is that di-carboxylic acid and polyol polyester reaction obtain polyester polyol, but this technology has following shortcoming
(1) production cycle long, be more than 20 hours reaction time;
(2) energy consumption is big, produces one ton of product consumed power more than 150 yuan;
(3) raw material availability is low, and the esterification rate during urethane is synthetic is below 82%;
(4) recovery of water is low in the production process, and one ton of product consume water is more than 0.5 ton.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, and a kind of raw material recycle is provided, have more light weight and wear-resisting, folding, oil resistant, chemically-resistant, and the significant ultra-low density polyurethane sole of effects of energy saving and emission reduction stoste synthesis technique.
For realizing above-mentioned purpose, technical scheme of the present invention is may further comprise the steps
(1) polyesterification reaction; Di-carboxylic acid and polyvalent alcohol are carried out under the composite catalyst effect, carrying out polyesterification reaction; Acquisition gathers adipic acid terephthalic acid ethylene glycol bisthioglycolate glycol ester (hereinafter to be referred as polyester polyol); Described composite catalyst includes acetate, triethylene diamine, stannous octoate/Si catalyst, and the amount of this composite catalyst catalyzer is 1:155-165 with respect to the ratio of the total mass of di-carboxylic acid and polyvalent alcohol;
(2) step (1) is obtained polyester polyol and mix acquisition A material with auxiliary material silicone oil; Step (1) is obtained polyester polyol and isocyanic ester and polyether glycol pre-polymerization obtain the B material.
Further setting is that the massfraction ratio of described foam stabilizer, grafted polyester and silicone oil is: 0.5:6:0.4.
Further being provided with is that described auxiliary material is a foam stabilizer silicone oil, and this foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1:3-5.
Further being provided with is that described di-carboxylic acid is: described di-carboxylic acid is adipic acid and terephthalic acid; And adipic acid and terephthalic acid mass ratio=1:1-3; Described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol, and terepthaloyl moietie and Diethylene Glycol mass ratio=1:1-5.
Further being provided with is that each set of dispense ratio of described composite catalyst does, in massfraction:
Acetate Potassium ethanoate 1-3 part, zinc acetate 1-8 part
Triethylene diamine 30-50 part
Stannous octoate/Si catalyst 30-50 part.
The invention has the advantages that: in new technology, adopt composite catalyst; To form novel complex catalyst system on the composite each other basis of acetate, triethylene diamine, stannous octoate/Si catalyst; Under new composite catalyst; Realized that the synthesis technique cycle is 16 hours, cut down the consumption of energy greatly, reduced cost.The concrete contrast as follows:
Tradition polyesterification technology:
Di-carboxylic acid+polyvalent alcohol---polyester polyol (the polyreaction cycle of polyester polyol is 20 hours, the polymerization rate 75% of polyester polyol, 1.2 tons/ton of water consumptions, 150 yuan/ton of power consumptions)
Polyesterification technology of the present invention:
Di-carboxylic acid+polyvalent alcohol+composite catalyst---polyester polyol (the polyreaction cycle of polyester polyol is the polymerization rate 85% of 16 hours polyester polyols, 0.5 ton/ton of water consumption, 120 yuan/ton of power consumptions).
(2) adopted full water foamedly, do not had oiliness, reduced pollution, reduced discharging greatly at synthetic intermediate.Improved the recovery of water, the consumption of one ton of product water is 0.5 ton in the new technology.
(3) under new technology, adopt new prescription, in polyester polyol, added isocyanic ester and polyether glycol and grafted polyester, reduce product molding density and improved utilization ratio of raw materials.The di-carboxylic acid of novel process and the utilization ratio of divalent alcohol are more than 85%.
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Through embodiment the present invention is carried out concrete description below; Only be used for the present invention is further specified; Can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
May further comprise the steps
(1) polyesterification reaction carries out under the composite catalyst effect, carrying out polyesterification reaction with di-carboxylic acid and polyvalent alcohol, obtains polyester polyol, and described composite catalyst includes acetate, triethylene diamine, stannous octoate/Si catalyst; The amount of this composite catalyst catalyzer is 1:155 with respect to the ratio of the total mass of di-carboxylic acid and polyvalent alcohol; This process using normal polyester reaction conditions gets final product, and described di-carboxylic acid is adipic acid and terephthalic acid, and described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol; And adipic acid and terephthalic acid mass ratio=1:1; Terepthaloyl moietie and Diethylene Glycol mass ratio=1:1, each set of dispense ratio of described composite catalyst do, in massfraction:
1 part of acetate Potassium ethanoate, 1 part of zinc acetate
30 parts of triethylene diamines
30 parts of stannous octoate/Si catalysts.
(2) step (1) is obtained polyester polyol and mix acquisition A material with auxiliary material, described auxiliary material is foam stabilizer and grafted polyester, and this foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1:3.；
(3) step (1) is obtained polyester polyol and isocyanic ester and polyether glycol pre-polymerization and obtain the B material.
Embodiment 2
May further comprise the steps
(1) polyesterification reaction; Di-carboxylic acid and polyvalent alcohol are carried out under the composite catalyst effect, carrying out polyesterification reaction, obtain polyester polyol, described composite catalyst includes acetate, triethylene diamine, stannous octoate/Si catalyst; The amount of this composite catalyst catalyzer is 1:160 with respect to the ratio of the total mass of di-carboxylic acid and polyvalent alcohol; This process using normal polyester reaction conditions gets final product, and described di-carboxylic acid is adipic acid and terephthalic acid, and described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol; And adipic acid and terephthalic acid mass ratio=1:1-2; Terepthaloyl moietie and Diethylene Glycol mass ratio=1:2.5, each set of dispense ratio of described composite catalyst do, in massfraction:
2.5 parts of acetate Potassium ethanoates, 5 parts of zinc acetates
40 parts of triethylene diamines
40 parts of stannous octoate/Si catalysts.
(2) step (1) is obtained polyester polyol and mix acquisition A material with auxiliary material, described auxiliary material is that foam stabilizer and grafted polyester are formed, and this foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1:4.；
(3) step (1) is obtained polyester polyol and isocyanic ester and polyether glycol pre-polymerization and obtain the B material.
Embodiment 3
May further comprise the steps
(1) polyesterification reaction; Di-carboxylic acid and polyvalent alcohol are carried out under the composite catalyst effect, carrying out polyesterification reaction, obtain polyester polyol, described composite catalyst includes acetate, triethylene diamine, stannous octoate/Si catalyst; The amount of this composite catalyst catalyzer is 1:165 with respect to the ratio of the total mass of di-carboxylic acid and polyvalent alcohol; This process using normal polyester reaction conditions gets final product, and described di-carboxylic acid is oxalic acid and terephthalic acid, and described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol; And adipic acid and terephthalic acid mass ratio=1:3; Terepthaloyl moietie and Diethylene Glycol mass ratio=1:5, each set of dispense ratio of described composite catalyst do, in massfraction:
3 parts of acetate Potassium ethanoates, 8 parts of zinc acetates
50 parts of triethylene diamines
50 parts of stannous octoate/Si catalysts.
(2) step (1) is obtained polyester polyol and mix acquisition A component with auxiliary material, described auxiliary material is that this foam stabilizer of foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1:5.；
(3) step (1) is obtained polyester polyol and isocyanic ester and polyether glycol pre-polymerization and obtain the B component.
Claims (5)
1. ultra-low density polyurethane sole stoste synthesis technique is characterized in that may further comprise the steps:
Polyesterification reaction; Di-carboxylic acid and polyvalent alcohol are carried out under the composite catalyst effect, carrying out polyesterification reaction; Obtain polyester polyol; Described composite catalyst includes acetate, triethylene diamine, stannous octoate/Si catalyst, and the amount of this composite catalyst catalyzer is 1:155-165 with respect to the ratio of the total mass of di-carboxylic acid and polyvalent alcohol;
Step (1) is obtained polyester polyol mix with auxiliary material, obtain the A component, this auxiliary material includes foam stabilizer, grafted polyester and silicone oil;
Step (1) is obtained polyester polyol and isocyanic ester and polyether glycol pre-polymerization obtain the B component, wherein the quality of isocyanic ester accounts for the 22-22.2% of summation of each raw material of B component.
2. a kind of ultra-low density polyurethane sole stoste synthesis technique according to claim 1, it is characterized in that: the massfraction ratio of described foam stabilizer, grafted polyester and silicone oil is: 0.5:6:0.4.
3. a kind of ultra-low density polyurethane sole stoste synthesis technique according to claim 1, it is characterized in that: described foam stabilizer includes following component, according to the mass fraction:
Octamethylcyclotetrasiloxane: polyether silicone 1:3-5.
4. a kind of ultra-low density polyurethane sole stoste synthesis technique according to claim 1 and 2; It is characterized in that: described di-carboxylic acid is adipic acid and terephthalic acid; And adipic acid and terephthalic acid mass ratio=1:1-3; Described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol, and terepthaloyl moietie and Diethylene Glycol mass ratio=1:1-5.
5. a kind of ultra-low density polyurethane sole stoste synthesis technique according to claim 3 is characterized in that: each set of dispense ratio of described composite catalyst does, in massfraction:
Acetate Potassium ethanoate 1-3 part, zinc acetate 1-8 part
Triethylene diamine 30-50 part
Stannous octoate/Si catalyst 30-50 part.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110242647 CN102329409A (en) | 2011-08-23 | 2011-08-23 | Synthesis process for ultralow-density polyurethane sole stoste |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110242647 CN102329409A (en) | 2011-08-23 | 2011-08-23 | Synthesis process for ultralow-density polyurethane sole stoste |
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| CN102329409A true CN102329409A (en) | 2012-01-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015062960A1 (en) * | 2013-10-28 | 2015-05-07 | Basf Se | Low density polyurethane microcellular elastomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486788A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| US20090253817A1 (en) * | 2008-04-03 | 2009-10-08 | Momentive Performance Materials, Inc. | Polyurethane foams containing silicone surfactants |
| CN101962432A (en) * | 2010-07-20 | 2011-02-02 | 温州市登达化工有限公司 | Synthesis process of low-density polyurethane sole stock solution |
-
2011
- 2011-08-23 CN CN 201110242647 patent/CN102329409A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090253817A1 (en) * | 2008-04-03 | 2009-10-08 | Momentive Performance Materials, Inc. | Polyurethane foams containing silicone surfactants |
| CN101486788A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| CN101962432A (en) * | 2010-07-20 | 2011-02-02 | 温州市登达化工有限公司 | Synthesis process of low-density polyurethane sole stock solution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015062960A1 (en) * | 2013-10-28 | 2015-05-07 | Basf Se | Low density polyurethane microcellular elastomer |
| CN105683236A (en) * | 2013-10-28 | 2016-06-15 | 巴斯夫欧洲公司 | Low density polyurethane microcellular elastomer |
| CN105683236B (en) * | 2013-10-28 | 2018-11-23 | 巴斯夫欧洲公司 | Low density polyurethane micropore elastomer |
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Application publication date: 20120125 |