CN101962432B - Synthesis process of low-density polyurethane sole stock solution - Google Patents
Synthesis process of low-density polyurethane sole stock solution Download PDFInfo
- Publication number
- CN101962432B CN101962432B CN2010102338461A CN201010233846A CN101962432B CN 101962432 B CN101962432 B CN 101962432B CN 2010102338461 A CN2010102338461 A CN 2010102338461A CN 201010233846 A CN201010233846 A CN 201010233846A CN 101962432 B CN101962432 B CN 101962432B
- Authority
- CN
- China
- Prior art keywords
- polyester polyol
- composite catalyst
- catalyst
- polyvalent alcohol
- low
- Prior art date
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 10
- 239000004814 polyurethane Substances 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 239000011550 stock solution Substances 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 21
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- 150000007520 diprotic acids Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- FHUOTRMCFQTSOA-UHFFFAOYSA-M potassium;acetic acid;acetate Chemical compound [K+].CC(O)=O.CC([O-])=O FHUOTRMCFQTSOA-UHFFFAOYSA-M 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 4
- 235000013904 zinc acetate Nutrition 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a synthesis process of a low-density polyurethane sole stock solution, which comprises the following steps of: carrying out a polyesterification reaction, subjecting diacid and polyalcohol to a 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 catalyst; mixing the obtained polyester polyol with auxiliary materials to obtain a component A; and prepolymerizing the obtained polyester polyol with isocyanate to obtain a component B. The invention has the advantages of obvious energy-saving and emission-reduction effect and high raw material utilization ratio.
Description
Technical field
The present invention relates to a kind of Chemicals synthesis technique, specifically be meant 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 diprotic acid and polyol polyester reaction obtain polyester polyol, but this technology has following shortcoming
(1) production cycle long, be more than 24 hours reaction time;
(2) energy consumption is big, produces one ton of product consumed power more than 200 yuan;
(3) raw material availability is low, and the esterification rate during urethane is synthetic is below 73%;
(4) recovery of water is low in the production process, and one ton of product consume water is more than 1.5 tons.
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, and the significant 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; Diprotic 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 with respect to the ratio of the total mass of diprotic acid and polyvalent alcohol: 175-195;
(2) step (1) is obtained polyester polyol and mix acquisition A material with auxiliary material; Step is obtained the B material with step (1) acquisition polyester polyol and isocyanic ester pre-polymerization.
Further being provided with is that described auxiliary material is a foam stabilizer, and this foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1: 2-10.
Further being provided with is that described diprotic acid is a hexanodioic acid, and 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 1-5 part, zinc acetate 1-10 part
Triethylene diamine 30-50 part
Stannous octoate/Si catalyst 30-70 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 20 hours, cut down the consumption of energy greatly, reduced cost.The concrete contrast as follows:
Tradition polyesterification technology:
Diprotic acid+polyvalent alcohol---polyester polyol (the polyreaction cycle of polyester polyol is 20 hours, the polymerization rate 75% of polyester polyol, 1.5 tons/ton of water consumptions, 200 yuan/ton of power consumptions)
Polyesterification technology of the present invention:
Diprotic acid+polyvalent alcohol+composite catalyst---polyester polyol (the polyreaction cycle of polyester polyol is the polymerization rate 83% of 20 hours polyester polyols, 1.1 tons/ton of water consumptions, 150 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 1.1 tons in the new technology.
(3) under new technology, adopt new prescription, in polyester polyol, added isocyanic ester, improved utilization ratio of raw materials.The diprotic acid of novel process and the utilization ratio of divalent alcohol are more than 83%.
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 diprotic 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: 175 with respect to the ratio of the total mass of diprotic acid and polyvalent alcohol; This process using normal polyester reaction conditions gets final product; Described diprotic acid is a hexanodioic acid, and described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol, and terepthaloyl moietie and Diethylene Glycol mass ratio=1: 1; Each set of dispense ratio of described composite catalyst does, 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 that this foam stabilizer of foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1: 2.；
(3) step is obtained the B material with step (1) acquisition polyester polyol and isocyanic ester pre-polymerization.
Embodiment 2
May further comprise the steps
(1) polyesterification reaction carries out under the composite catalyst effect, carrying out polyesterification reaction with diprotic acid and polyvalent alcohol, obtains polyester polyol; Described composite catalyst includes acetate, triethylene diamine, stannous octoate/Si catalyst; The amount of this composite catalyst catalyzer is 1: 195 with respect to the ratio of the total mass of diprotic acid and polyvalent alcohol, and this process using normal polyester reaction conditions gets final product, and described diprotic acid is a hexanodioic acid; Described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol; And 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
50 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 this foam stabilizer of foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1: 6.；
(3) step is obtained the B material with step (1) acquisition polyester polyol and isocyanic ester pre-polymerization.
Embodiment 3
May further comprise the steps
(1) polyesterification reaction carries out under the composite catalyst effect, carrying out polyesterification reaction with diprotic acid and polyvalent alcohol, obtains polyester polyol; Described composite catalyst includes acetate, triethylene diamine, stannous octoate/Si catalyst; The amount of this composite catalyst catalyzer is 1: 185 with respect to the ratio of the total mass of diprotic acid and polyvalent alcohol, and this process using normal polyester reaction conditions gets final product, and described diprotic acid is a hexanodioic acid; Described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol; And terepthaloyl moietie and Diethylene Glycol mass ratio=1: 5, each set of dispense ratio of described composite catalyst do, in massfraction:
5 parts of acetate Potassium ethanoates, 10 parts of zinc acetates
50 parts of triethylene diamines
70 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 this foam stabilizer of foam stabilizer includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1: 10.；
(3) step is obtained the B material with step (1) acquisition polyester polyol and isocyanic ester pre-polymerization.
Claims (2)
1. low-density polyurethane sole stoste synthesis technique is characterized in that may further comprise the steps:
(1) polyesterification reaction; Diprotic 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 and stannous octoate/Si catalyst, and the amount of this composite catalyst catalyzer is 1 with respect to the ratio of the total mass of diprotic acid and polyvalent alcohol: 175-195, described diprotic acid are hexanodioic acid; Described polyvalent alcohol is the mixture of terepthaloyl moietie and Diethylene Glycol, and terepthaloyl moietie and Diethylene Glycol mass ratio=1: 1-5;
(2) step (1) is obtained polyester polyol and mix acquisition A material with auxiliary material, described auxiliary material is a foam stabilizer, includes following component, according to the mass fraction, and octamethylcyclotetrasiloxane: polyether silicone=1: 2-10;
(3) step (1) acquisition polyester polyol and isocyanic ester pre-polymerization are obtained the B material.
2. a kind of low-density polyurethane sole stoste synthesis technique according to claim 1 is characterized in that: each set of dispense ratio of described composite catalyst does, in massfraction:
Acetate Potassium ethanoate 1-5 part, zinc acetate 1-10 part
Triethylene diamine 30-50 part
Stannous octoate/Si catalyst 30-70 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102338461A CN101962432B (en) | 2010-07-20 | 2010-07-20 | Synthesis process of low-density polyurethane sole stock solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102338461A CN101962432B (en) | 2010-07-20 | 2010-07-20 | Synthesis process of low-density polyurethane sole stock solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101962432A CN101962432A (en) | 2011-02-02 |
| CN101962432B true CN101962432B (en) | 2012-05-16 |
Family
ID=43515494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102338461A Active CN101962432B (en) | 2010-07-20 | 2010-07-20 | Synthesis process of low-density polyurethane sole stock solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101962432B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329409A (en) * | 2011-08-23 | 2012-01-25 | 温州市登达化工有限公司 | Synthesis process for ultralow-density polyurethane sole stoste |
| CN102417588B (en) * | 2011-11-18 | 2013-06-05 | 温州大学 | Polyester polyurethane sole stoste and preparation method thereof |
| CN102516484A (en) * | 2011-12-15 | 2012-06-27 | 温州市登达化工有限公司 | Synthesis process of polyurethane stock solution for energy-saving heat-insulation nano wall |
| CN108003319B (en) * | 2017-12-14 | 2020-09-11 | 山东一诺威聚氨酯股份有限公司 | Composite material for high-cohesiveness double-density polyurethane sole product and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148493A (en) * | 2007-10-31 | 2008-03-26 | 无锡双象化学工业有限公司 | Polyester type ultra-low density polyurethane resin for shoes |
| CN101328254A (en) * | 2008-07-29 | 2008-12-24 | 浙江华峰新材料股份有限公司 | Polyester type polyurethane micropore elastomer added with low cost polycarbonate polyatomic alcohol and preparation thereof |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8044109B2 (en) * | 2008-04-03 | 2011-10-25 | Momentive Performance Materials Inc. | Polyurethane foams containing silicone surfactants |
-
2010
- 2010-07-20 CN CN2010102338461A patent/CN101962432B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148493A (en) * | 2007-10-31 | 2008-03-26 | 无锡双象化学工业有限公司 | Polyester type ultra-low density polyurethane resin for shoes |
| CN101328254A (en) * | 2008-07-29 | 2008-12-24 | 浙江华峰新材料股份有限公司 | Polyester type polyurethane micropore elastomer added with low cost polycarbonate polyatomic alcohol and preparation thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101962432A (en) | 2011-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101962432B (en) | Synthesis process of low-density polyurethane sole stock solution | |
| CN107418501A (en) | The biodegradable UV curing adhesives of vegetable oil-based polyols type and preparation method | |
| CN104017533B (en) | Roof of the vehicle monocomponent moisture cure urethanes adhesive and preparation method thereof | |
| CN102241956A (en) | Poly(propylene carbonate)-based water-borne polyurethane adhesive and preparation method thereof | |
| CN101362818B (en) | Method for preparing biodegradable polyurethane rigid foam from bamboo waste liquefaction products | |
| CN109554101A (en) | A kind of polyurethane water-proof paint | |
| CN101050265B (en) | Wet mild polyurethane resin in use for synthetic leather, and preparation method | |
| CN104893645A (en) | Polyurethane plastic runway adhesive and preparation method thereof | |
| CN102816551A (en) | Ultraviolet (UV)-moisture double-curing liquid optical transparent adhesive and preparation method thereof | |
| CN102838717A (en) | Preparation of thermoplastic polyurethane elastomer with polypropylene carbonate as soft segment | |
| CN104130378B (en) | Silane-modified dual-component polyurethane court plastic sizing agent and preparation method thereof | |
| CN101805588A (en) | Polyurethane road caulking sealant with good durability and production process | |
| CN101985542B (en) | Wind blade coating and preparation method thereof | |
| CN102417588B (en) | Polyester polyurethane sole stoste and preparation method thereof | |
| CN103289056A (en) | Method for producing high-hydroscopicity soft polyurethane foam through bamboo fiber polyhydric alcohol | |
| CN105153397A (en) | Preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather | |
| CN102532930B (en) | A kind of modified vinyl resin and preparation method thereof | |
| CN101899261A (en) | Paint for painting high-speed train | |
| CN102329409A (en) | Synthesis process for ultralow-density polyurethane sole stoste | |
| CN102399524A (en) | Glue for producing car ceiling with wet method | |
| CN102220104A (en) | Railway ballast adhesive and its preparation method and application | |
| CN101125819A (en) | Method for synthesizing primary octadecylamine polyoxyethylene ether | |
| CN102731757A (en) | Preparation method of water-soluble copolyester for textile size | |
| CN101857722A (en) | Wet-type ironing color-changing polyurethane resin and preparation method thereof | |
| CN101798482A (en) | Environment-friendly aqueous adhesive for shoes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Synthesis process of low-density polyurethane sole stock solution Effective date of registration: 20120621 Granted publication date: 20120516 Pledgee: Bank of Wenzhou Limited by Share Ltd. Liming branch Pledgor: WENZHOU DENGDA CHEMICAL Co.,Ltd. Registration number: 2012990000316 |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20150618 Granted publication date: 20120516 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20151218 Granted publication date: 20120516 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20160204 Granted publication date: 20120516 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20160804 Granted publication date: 20120516 |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20160811 Granted publication date: 20120516 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20170211 Granted publication date: 20120516 |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20170517 Granted publication date: 20120516 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20171117 Granted publication date: 20120516 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240204 Address after: No. 99 Shangqin Road, Lucheng District, Wenzhou City, Zhejiang Province, 325000 Patentee after: Wenzhou Dongye Electronic Technology Co.,Ltd. Country or region after: China Address before: 325000 China Shoes Capital Phase III, Lucheng District, Wenzhou City, Zhejiang Province Patentee before: WENZHOU DENGDA CHEMICAL Co.,Ltd. Country or region before: China |