CN102557897B - Plant-phenol-based polyether polyol - Google Patents
Plant-phenol-based polyether polyol Download PDFInfo
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- CN102557897B CN102557897B CN201110327942.7A CN201110327942A CN102557897B CN 102557897 B CN102557897 B CN 102557897B CN 201110327942 A CN201110327942 A CN 201110327942A CN 102557897 B CN102557897 B CN 102557897B
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- plant
- phenol
- polyether glycol
- polyether polyol
- plant phenols
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 32
- 229920000570 polyether Polymers 0.000 title claims abstract description 32
- 229920005862 polyol Polymers 0.000 title abstract 5
- 150000003077 polyols Chemical class 0.000 title abstract 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 52
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 26
- 150000002989 phenols Chemical class 0.000 claims description 25
- 241000196324 Embryophyta Species 0.000 abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 244000226021 Anacardium occidentale Species 0.000 abstract description 5
- 235000020226 cashew nut Nutrition 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- -1 bisphenol compound Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 244000044283 Toxicodendron succedaneum Species 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 229960004249 sodium acetate Drugs 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 0 *C1C=C(*)C=C(*)C1 Chemical compound *C1C=C(*)C=C(*)C1 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses plant-phenol-based polyether polyol. One or more monophenol or bisphenol compounds which have a long carbon chain or a mixture of the monophenol or bisphenol compounds in cashew nut shell oil or other similar plant phenol can be used as the raw materials of plant phenol. The plant-phenol-based polyether polyol can be obtained under an appropriate reaction condition and the action of a catalyst. The viscosity of the polyether polyol is less than or equal to 25,000CPS; a hydroxyl value is 200 to 600; and an acid value is less than 5. The plant-phenol-based polyether polyol can be completely biodegraded possibly.
Description
Technical field
The present invention relates to a kind of polyether glycol, particularly a kind of polyether glycol based on plant phenols.The raw material of this plant phenols can comprise cashew nut shell oil and other similar plant phenols based on natural phant.
Background technology
Traditional polyether glycol all derives from petroleum chemicals or is obtained by reacting, and along with the growth of the demand to this Nonrenewable resources of oil and the exhaustion of resource itself, oil price is constantly bettered a record.Simultaneously along with people progressively strengthen the consciousness of renewable resources, some vegetables oil deriving from plant are more and more subject to people's attention as the substitute of petroleum derivative.
Plant phenols is as a kind of natural product, and its raw material sources can comprise cashew nut shell oil based on natural phant, lacquer tree phenol, and other similar plants.Its main component is a kind of single phenol with Long carbon chain or bisphenol compound, the chemical structure special because of it and the special physics-chem characteristic brought thus, make it while replacing the phenol based on oil, additionally provide the advantage of other improvement a lot of and modification.
Summary of the invention
Technical problem to be solved by this invention provides a kind of polyether glycol based on plant phenols for the problem existing for existing polyether glycol.The raw material of this plant phenols can be with cashew nut shell oil, lacquer tree phenol, and one or more single phenol with Long carbon chain of providing of other similar plant phenols or bisphenols chemical combination or mixture.Can should obtain under appropriate reaction condition and under the effect of catalyzer based on the polyether glycol of plant phenols.
Technical problem to be solved by this invention can be achieved through the following technical solutions:
Based on a polyether glycol for plant phenols, the polyether glycol for following general formula (1):
Wherein, R
1a can be selected from alone, R
2can be selected from H or A alone, A is
n=1-15, R
3be selected from H.
In a preferred embodiment of the invention, described R
2independently be selected from:
Described polyether glycol brookfield viscosity≤25,000CPS, hydroxyl value is 200-600, acid number: lower than 5.
In a preferred embodiment of the invention, described polyether glycol brookfield viscosity is preferably 10,000-22,000CPS; Described hydroxyl value is 350-400.
Plant phenols of the present invention is be selected from cardanol, lacquer tree phenol or other similar plant phenols.
Described cardanol is obtained through rectifying or molecular distillation by cashew nut shell oil.
Polyether glycol based on plant phenols of the present invention has complete biodegradable possibility.Can be used for preparing soft bubble, hard-foam polyurethane elastomerics.The present invention has thermotolerance, rigidity, physical strength, oxygen index and the water tolerance better than conventional polyether type polyvalent alcohol; Having again the resistance to acids and bases than normal polyester type polyvalent alcohol and toughness, is an excellent comprehensive performance simultaneously with polyether-type and polyester polyol, makes up again the comprehensive polyvalent alcohol of the shortcoming of polyether-type and polyester polyol.
Embodiment
Although listed the chemical structure of the polyether glycol based on plant phenols of the present invention above, these have been enumerated and have been only used to citing and explanation.Except claim limits, those skilled in the art do not surmount essence of the present invention and invention exemplify the scope of structure, can much change of the present invention and make a variation.
Polyether glycol based on plant phenols of the present invention can obtain according to different plant phenols raw materials.Three examples are only used for illustrating the feasible embodiment of many kinds below.
Embodiment 1:
In glass reactor, stir the oxalic acid and the 50 grams of cardanols (0.17 mole) that add 7.82 grams (0.17 moles), be cooled to 0 degree Celsius; With dropping funnel, the hydrogen peroxide of 38.5 grams of (0.34 moles) 30% is added drop-wise in reactor under cooling while stirring, controls temperature of reactor and be no more than 0 degree Celsius, time for adding, at 5-10 hour, adopts cooling bath temperature control.
After dropwise reaction terminates, temperature of reaction is raised to 35 degree Celsius, epoxy group(ing) is allowed to be hydrolyzed into formyl hydroxy ester, half ester Celsius 80 degree of hydrolysis in four hours under sodium-acetate of such generation, after product cleans to neutrality with the neutralization of excessive water, cleaning adopts separating funnel to carry out, then uses anhydrous sodium sulfate drying, the intermediate product obtained.
Obtained intermediate product is joined in ethoxylation still, then adds 0.1 gram, potassium hydroxide and 7.8 grams, oxyethane and react, react after 45 minutes, obtain the polyether glycol 60 grams based on plant phenols of following structural formula:
The brookfield viscosity of the polyether glycol based on plant phenols of the as above structural formula obtained is 13,000, and hydroxyl value is 400, and acid number is lower than 5.
Embodiment 2:
The oxalic acid and the 150 grams of cardanols (0.5 mole) that add 20 grams (0.57 moles) are stirred in glass reactor, be cooled to 0 degree Celsius, with dropping funnel, the hydrogen peroxide of 116 grams of (1.02 moles) 30% is added drop-wise in reactor under cooling while stirring, control temperature of reactor and be no more than 0 degree Celsius, time for adding, at 5-10 hour, adopts cooling bath temperature control.
After dropwise reaction terminates, temperature of reaction is raised to 35 degree Celsius, epoxy group(ing) is allowed to be hydrolyzed into formyl hydroxy ester, half ester Celsius 80 degree of hydrolysis in four hours under sodium-acetate of such generation, after product cleans to neutrality with the neutralization of excessive water, cleaning adopts separating funnel to carry out, then uses anhydrous sodium sulfate drying, the intermediate product obtained.
Obtained intermediate product is joined after in ethoxylation still, then adds 0.3 gram, potassium hydroxide and 125 grams, oxyethane and react, react after 45 minutes, obtain the polyether glycol 199 grams based on plant phenols of following structural formula:
The brookfield viscosity of the polyether glycol based on plant phenols of the as above structural formula obtained is 16,000CPS, and hydroxyl value is 380, and acid number is lower than 5
Embodiment 3:
The oxalic acid and the 150 grams of cardanols (0.5 mole) that add 19 grams (0.6 moles) are stirred in glass reactor, be cooled to 0 degree Celsius, with dropping funnel, the hydrogen peroxide of 115 grams of (1.02 moles) 30% is added drop-wise in reactor under cooling while stirring, control temperature of reactor between 24-32 degree Celsius, time for adding, at 5-10 hour, adopts cooling bath temperature control.
After dropwise reaction terminates, temperature of reaction is raised to 35 degree Celsius, epoxy group(ing) is allowed to be hydrolyzed into formyl hydroxy ester, half ester Celsius 80 degree of hydrolysis in four hours under sodium-acetate of such generation, after product cleans to neutrality with the neutralization of excessive water, cleaning adopts separating funnel to carry out, then with the intermediate product that anhydrous sodium sulphate obtains.
Obtained intermediate product is joined after in ethoxylation still, then adds 0.3 gram, potassium hydroxide and propylene oxide 56 grams and react, react after 55 minutes, obtain the polyether glycol 112 grams based on plant phenols of following structural formula:
The brookfield viscosity of the polyether glycol based on plant phenols of the as above structural formula obtained is 10,000CPS, and hydroxyl value is 390, and acid number is lower than 5.
Claims (3)
1. based on a polyether glycol for plant phenols, the polyether glycol for following general formula (1):
Wherein, R
1be selected from A alone, A is
n=1-15, R
3be selected from H;
Described R
2independently be selected from:
2., as claimed in claim 1 based on the polyether glycol of plant phenols, it is characterized in that, described polyether glycol brookfield viscosity≤25,000CPS, hydroxyl value is 200-600, acid number: lower than 5.
3., as claimed in claim 1 based on the polyether glycol of plant phenols, it is characterized in that, described polyether glycol brookfield viscosity is preferably 10,000-22,000 CPS; Described hydroxyl value is 350-400.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110327942.7A CN102557897B (en) | 2011-10-25 | 2011-10-25 | Plant-phenol-based polyether polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110327942.7A CN102557897B (en) | 2011-10-25 | 2011-10-25 | Plant-phenol-based polyether polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102557897A CN102557897A (en) | 2012-07-11 |
| CN102557897B true CN102557897B (en) | 2015-02-25 |
Family
ID=46404678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110327942.7A Active CN102557897B (en) | 2011-10-25 | 2011-10-25 | Plant-phenol-based polyether polyol |
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| Country | Link |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3074443B1 (en) * | 2013-11-27 | 2018-11-21 | Dow Global Technologies LLC | Cardanol modified epoxy polyol and corresponding polyurethane |
| WO2015077944A1 (en) * | 2013-11-27 | 2015-06-04 | Dow Global Technologies Llc | Cardanol modified epoxy polyol |
| CN110578261B (en) * | 2019-09-11 | 2021-11-23 | 苏州联胜化学有限公司 | Polyester type terylene anti-sticking soaping agent and preparation method thereof |
| CN114524927A (en) * | 2022-03-08 | 2022-05-24 | 上海回天新材料有限公司 | Preparation method of cardanol bio-based polyol and application of cardanol bio-based polyol in flexible packaging adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2889297A (en) * | 1953-06-29 | 1959-06-02 | Atlas Powder Co | Polyvinyl acetate adhesive compositions containing a polyethylene glycol monoether of a monohydric phenol |
| CN101687967A (en) * | 2007-05-29 | 2010-03-31 | 汉森集团公司 | Be applicable to the composition of golf ball |
-
2011
- 2011-10-25 CN CN201110327942.7A patent/CN102557897B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2889297A (en) * | 1953-06-29 | 1959-06-02 | Atlas Powder Co | Polyvinyl acetate adhesive compositions containing a polyethylene glycol monoether of a monohydric phenol |
| CN101687967A (en) * | 2007-05-29 | 2010-03-31 | 汉森集团公司 | Be applicable to the composition of golf ball |
Non-Patent Citations (1)
| Title |
|---|
| Aromatic Glycols;ANTHONYJ. SHUKIS等;《Journal of the American Chemical Society》;19440930;第66卷;第1461-1462页 * |
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| Publication number | Publication date |
|---|---|
| CN102557897A (en) | 2012-07-11 |
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Owner name: CHANGSHU NAISU BIOMATERIALS TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: NAIS CO., LTD. Effective date: 20131106 Free format text: FORMER OWNER: GUANGZHOU YULI CHEMICAL CO., LTD. BEIJING ORIENTAL CLEARSKY TECHNOLOGY CO., LTD. Effective date: 20131106 |
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Free format text: CORRECT: ADDRESS; TO: 215500 SUZHOU, JIANGSU PROVINCE |
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Effective date of registration: 20131106 Address after: 215500 Changshu Province, Jiangsu Province, new materials Industrial Park Road, Yu Sheng, No. 26 Applicant after: Changshu Naisu Biological Material Technology Co., Ltd. Address before: Lewis, 16192, coast road, Delaware Applicant before: Naisu Co., Ltd. Applicant before: Guangzhou Yuli Chemical Co., Ltd. Applicant before: Beijing Dongfangqingkong Technology Co., Ltd. |
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