CN101628963B - Bicomponent for manufacturing polyester polyurethane woodlike material - Google Patents
Bicomponent for manufacturing polyester polyurethane woodlike material Download PDFInfo
- Publication number
- CN101628963B CN101628963B CN2009101159940A CN200910115994A CN101628963B CN 101628963 B CN101628963 B CN 101628963B CN 2009101159940 A CN2009101159940 A CN 2009101159940A CN 200910115994 A CN200910115994 A CN 200910115994A CN 101628963 B CN101628963 B CN 101628963B
- Authority
- CN
- China
- Prior art keywords
- polyvalent alcohol
- diethylene glycol
- acid ester
- adipic acid
- polyoxyethylene glycol
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a bicomponent used for manufacturing a polyester polyurethane woodlike material, wherein raw material formula of the polyhydric alcohol component mainly comprises polyester polyol, micromolecular dibasic alcohol taken as chain extender, catalyst, foaming agent and foam stabilizer and further comprises an additive agent; and the additive agent is a mixture formed by mixing three components of calcium stearate, nanometer calcium carbonate and micromolecular polyester polyol by a mechanical method, and the polyester polyol is formed by polyethylene glycol diethylene glycol adipate polyhydric alcohol and polyethylene glycol diethylene glycol phthalic anhydride adipate polyhydric alcohol. The polyester polyurethane woodlike material manufactured by the polyalcohol component added with the special additive agent and the specific polyester polyol and the like has the advantages of excellent performance, high strength, good dimensional stability and good wear resistance, can be suitable for producing various woodlike material products with higher requirements on the production intensity, such as shoe bottoms, furniture, and the like, and has wider application range.
Description
Technical field
The invention belongs to the polyurethane material field, particularly be used to make two components of polyester polyurethane woodlike material.
Background technology
Along with development of times, current society increases day by day to the demand of timber, but the forest reserves or timber resources are very limited, and people begin to try to adopt macromolecular material to substitute wood materials, substitute timber as having developed the polyurethane imitation wood material at present.Urethane is a kind of emerging and the most widely used a kind of macromolecular material, owing to polyurethane product hardness can be regulated, and the non-constant width of density range, be fit to very much produce the product that substitutes timber.
Existing polyurethane imitation wood material generally is divided into polyether-type and polyester type two classes, (tension stress intensity, tearing toughness are all relatively poor yet the intensity of existing polyurethane imitation wood material is relatively poor, be highly brittle), not wear-resisting and dimensional stability is bad, easy deformation and damage in transportation, therefore generally can only be used to produce to intensity and the not high goods of dimensional requirement, such as finishing material, photo frame, flowerpot etc., use range is very limited, generally can't be applied to shoe industry, upholstery etc.
In addition, the density range of the polyurethane imitation wood material in the existing technology is generally at 0.35g/cm
3～xxxg/cm
3, generally can't produce low-density polyurethane imitation wood material, when density is lower than 0.35g/cm
3The time, material hardness is very poor, easily shrinks, and dimensional stability is very poor, and the scope of application is very limited.
Summary of the invention
In order to solve above technical problem, one aspect of the present invention provides a kind of polyol component that is used to make polyester polyurethane woodlike material, the composition of raw materials of described polyol component mainly comprises polyester polyol, as small molecules dibasic alcohol, catalyzer, whipping agent and the foam stabilizer of chainextender, wherein, described composition of raw materials also comprises a kind of additive; This additive is the mixture that calcium stearate, nanometer grade calcium carbonate, three kinds of compositions of small molecules polyester polyol mix formation mechanically; Described polyester polyol is made up of polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol, and described small molecules polyvalent alcohol is made up of ethylene glycol and diethanolamine, and described catalyzer is a triethylene diamine; Described whipping agent is a water; Described foam stabilizer is a dimethyl siloxane.
Described mechanical system is meant that the mode with the pure physics in other words of pure machinery mixes described three kinds of compositions, for example three kinds of compositions is mixed, and carries out stirring and evenly mixing, perhaps stirs to add the grinding mixing.
Described nanometer grade calcium carbonate (nano level adopts international standard, promptly less than 100nm with the interior nano level that is called) is meant the calcium carbonate powder of powder median size less than 100nm.
Preparation method well-known to those skilled in the art is adopted in the preparation of described polyol component, in general, and can be with each composition of raw materials mixture by a certain percentage, and stir for some time at a certain temperature, just can make polyol component.Reaction conditionss such as the formula rate of the polyester polyol that those skilled in the art can require to select in the preparation process and adopted according to concrete goods, small molecules polyvalent alcohol, catalyzer, whipping agent, foam stabilizer and temperature of reaction, time.Polyester polyol, chainextender, catalyzer, whipping agent and foam stabilizer are the conventional raw material in the polyol component of making polyester polyurethane woodlike material, and the proportioning of these materials should be well-known to those skilled in the art.
Described polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol are common polyester polyol.The synthesis material of polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol is ethylene glycol, Diethylene Glycol, hexanodioic acid.The synthesis material of polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol is ethylene glycol, Diethylene Glycol, phthalic anhydride, hexanodioic acid.The preparation method of these two kinds of polyester polyols can adopt the preparation method of polyester polyol well-known to those skilled in the art.
Adopt the polyol component of technique scheme, the contriver is through a large amount of experimental studies, develop above-mentioned this special additive, wherein add the polyol component of this special additive, (comprise polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol in conjunction with the polyester polyol that adds particular combinations again, especially introduced phenyl ring in a kind of polyester polyol in back), and corresponding chainextender, foam stabilizer, catalyzer etc., the excellent performance of the polyester polyurethane woodlike material that made comes out: intensity height (tension stress intensity, tearing toughness, modulus all improves greatly, embrittlement not), dimensional stability is very good, wear resistance is also fine, go for the imitated wood material goods that production intensity is had relatively high expectations, such as sole, products such as furniture, range of application is wider; In addition, adopt this polyol component, can produce density range and be about 0.25g/cm
3～1.10g/cm
3Polyester polyurethane woodlike material, range of application can be wider.
As further improvement in the technical proposal, described additive is that calcium stearate, nanometer grade calcium carbonate, molecular weight are the mixture that 560～630 PDEGA polyvalent alcohol mixes formation mechanically.
Preferably, described calcium stearate, nanometer grade calcium carbonate, molecular weight are that the weight ratio between 560～630 the PDEGA polyvalent alcohol three is 1: 1: 1.
The add-on of described additive, those skilled in the art can require to select the add-on of additive according to concrete goods, and in general the amount of Jia Ruing is many more, and the intensity of goods is high more, preferably, the add-on of additive accounts for 25%～40% of described polyol component weight.
Preferably, the molecular weight of described polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol is 1450～1550; The molecular weight of described polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol is 1150～1250.
Further preferred, the mass ratio of described polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and described polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol is 1: 2～1: 3.
The base polyurethane prepolymer for use as component that is used to make polyester polyurethane woodlike material that the present invention also provides a kind of and above-mentioned polyol component to be used on the other hand, the composition of raw materials of described base polyurethane prepolymer for use as component comprises polyester polyol, isocyanic ester, wherein, described polyester polyol is a polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol; Described different hydrogen acid ether is 4,4-ditan-2-isocyanic ester.
Described base polyurethane prepolymer for use as component can also adopt other any base polyurethane prepolymer for use as components of making polyester polyurethane woodlike material that can be used in well known to those skilled in the art.Preparation method well-known to those skilled in the art is adopted in the preparation of this component, in general, and can be with each composition of raw materials mixture by a certain percentage, and stir for some time at a certain temperature, just can make the base polyurethane prepolymer for use as component.Reaction conditionss such as the polyester polyol that those skilled in the art can require to select in the preparation process and adopted according to concrete goods, the formula rate of isocyanic ester and temperature of reaction, time.
The present invention also provides a kind of two components that are used to make polyester polyurethane woodlike material on the other hand, and its two components by coupling are formed, and described two components are above-mentioned polyol component and above-mentioned base polyurethane prepolymer for use as component.
The present invention also provides a kind of polyester polyurethane woodlike material on the other hand, and it is mixed by a certain percentage by above-mentioned polyol component and above-mentioned base polyurethane prepolymer for use as component and reacts and make.The preparation method of polyurethane sole materials adopts method well-known to those skilled in the art, reaction conditionss such as the temperature of the blending ratio of polyol component and base polyurethane prepolymer for use as component and reaction, time, those skilled in the art can select according to concrete product requirements.
Embodiment
Below be specific embodiments of the invention, technical scheme of the present invention is further described, but the present invention is not limited to these embodiment.
Embodiment 1:
1, the preparation of polyester polyol can be adopted conventional polyester polyol preparation method, originally is to adopt the nitrogen voltage drop method to prepare among the embodiment.
Molecular weight is about the preparation process of 1500 polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol:
In reactor, add ethylene glycol 50g, Diethylene Glycol 50g, hexanodioic acid 90g successively, open stirring, begin to heat up, 1 hour stable dewatering speed of constant temperature (passes through rectifying tower when being warming up to 135～140 ℃, tower top temperature keeps＜102 ℃) follow-up temperature of continuing rising, be warming up to 180 ℃ of left and right sides nitrogen and switch, and progressively strengthen nitrogen amount and strengthen dehydration from the bottom feeding.Be warming up to 225 ± 5 ℃ of constant temperature, constant temperature adds catalyzer and begins to vacuumize after 1 hour, carry out transesterify, got a sample middle control analysis in per 2 hours to final acid number＜1 from vacuumizing after picking up counting 4 hours, hydroxyl value is 53～59, recovers normal pressure, and nitrogen switches top and feeds, begin the cooling, be cooled to 120 ℃ can take a sample do final analysis and the packing.
Molecular weight is the preparation process of 1200 polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol:
The preparation method is with polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol, and raw material is ethylene glycol 50 grams, Diethylene Glycol 50 grams, phthalic anhydride 20 grams, hexanodioic acid 65 grams.
2, the preparation of additive:
Be that 600 PDEGA polyvalent alcohol mixes by mass ratio at 1: 1: 1 with calcium stearate, nanometer grade calcium carbonate powder (the powder median size is about 60nm), molecular weight, stir evenly, grind to form paste through shredder and get final product.
3, synthesis of polyurethane performed polymer component:
Raw material: molecular weight is about 1500 polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol 18g, isocyanic ester 30g;
Add isocyanic ester and polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol successively to reactor, temperature of reaction kettle is controlled at 70-80 ℃, react and survey the NCO equivalent after 3 hours; Adjust NCO equivalent to 220, promptly make the base polyurethane prepolymer for use as component.
4, synthetic polyol component:
Raw material: it is the additive 30g that 1200 polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol 30g, ethylene glycol 18g, diethanolamine 0.5g, distilled water 0.8g, dimethyl siloxane 0.4g, triethylene diamine 0.8g, aforesaid method make that molecular weight is about 1500 polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol 12g, molecular weight;
In another reactor, add polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol, polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol, ethylene glycol, diethanolamine, distilled water, dimethyl siloxane, triethylene diamine, additive successively, temperature of reaction kettle is controlled at 50-60 ℃, stir and survey moisture after one hour, adjust the qualified back of moisture (moisture is approximately 0.55%), promptly make the polyvalent alcohol component.
Application example (synthesizing at the bottom of the imitative sabot):
Above-mentioned base polyurethane prepolymer for use as component that makes and polyvalent alcohol component are preheated to 40 ℃ respectively, together pour into again in the batch can of sole casting molding machine, circulated 20 minutes; Make a little test glass, the affirmation test glass is a foamed core.
Footwear mould (the footwear mould of sole) temperature is controlled at 50-70 ℃, the raw material of accomplishing fluently in the batch can is injected the footwear mould, 50-70 ℃ was vulcanized 5 minutes, and can take out sole.
Prepared sole density is 0.3g/cm3, and hardness is Shao Shi 93A.The intensity height, dimensional stability is very good, wear resistance is also fine, light, is suitable for soles such as the high sloping footwear of high-grade woman, beach shoes, geta.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (6)
1. polyol component that is used to make polyester polyurethane woodlike material, the composition of raw materials of described polyol component mainly comprises polyester polyol, as small molecules dibasic alcohol, catalyzer, whipping agent and the foam stabilizer of chainextender, it is characterized in that: described composition of raw materials also comprises a kind of additive; This additive is that calcium stearate, nanometer grade calcium carbonate, molecular weight are the mixture that three kinds of compositions of PDEGA polyvalent alcohol of 560～630 mix formation mechanically, the add-on of described additive account for described polyol component the composition of raw materials gross weight 25%～40%;
Described polyester polyol is made up of polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol, and described small molecules dibasic alcohol is made up of ethylene glycol and diethanolamine, and described catalyzer is a triethylene diamine; Described whipping agent is a water; Described foam stabilizer is a dimethyl siloxane.
2. polyol component according to claim 1 is characterized in that: described calcium stearate, nanometer grade calcium carbonate, molecular weight are that the weight ratio between 560～630 the PDEGA polyvalent alcohol three is 1: 1: 1.
3. polyol component according to claim 1 and 2 is characterized in that: the molecular weight of described polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol is 1450～1550; The molecular weight of described polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol is 1150～1250.
4. polyol component according to claim 3 is characterized in that: the mass ratio of described polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and described polyoxyethylene glycol Diethylene Glycol phthalic anhydride adipic acid ester polyvalent alcohol is 1: 2～1: 3.
5. two components that are used to make polyester polyurethane woodlike material, its two components by coupling are formed, described two components are described polyol component of claim 1 and base polyurethane prepolymer for use as component, the composition of raw materials of described base polyurethane prepolymer for use as component comprises polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and 4,4 '-diphenylmethanediisocyanate.
6. polyester polyurethane woodlike material, it is mixed by a certain percentage by described polyol component of claim 1 and base polyurethane prepolymer for use as component and reacts and make, wherein, the composition of raw materials of described base polyurethane prepolymer for use as component comprises polyoxyethylene glycol Diethylene Glycol adipic acid ester polyvalent alcohol and 4,4 '-diphenylmethanediisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101159940A CN101628963B (en) | 2009-08-17 | 2009-08-17 | Bicomponent for manufacturing polyester polyurethane woodlike material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101159940A CN101628963B (en) | 2009-08-17 | 2009-08-17 | Bicomponent for manufacturing polyester polyurethane woodlike material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101628963A CN101628963A (en) | 2010-01-20 |
| CN101628963B true CN101628963B (en) | 2011-04-13 |
Family
ID=41574254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101159940A Expired - Fee Related CN101628963B (en) | 2009-08-17 | 2009-08-17 | Bicomponent for manufacturing polyester polyurethane woodlike material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101628963B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558832B (en) * | 2010-12-15 | 2014-03-26 | 峰盈高分子材料(惠东)有限公司 | High-viscosity and multiple-component polyurethane container and manufacturing method of high-viscosity and multiple-component polyurethane container |
| CN111909415A (en) * | 2020-08-24 | 2020-11-10 | 惠阳富顺新型材料有限公司 | Environment-friendly pore-forming agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781962A (en) * | 2004-12-03 | 2006-06-07 | 赵亚娟 | Method for producing polyurethane resin for synthetic leather |
| CN101381448A (en) * | 2008-10-14 | 2009-03-11 | 太仓市旭川树脂有限公司 | Polyurethane resin for water proof and breathable clothing leather |
| CN101486801A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density polyurethane micropore elastomer added with thermal foamable microsphere and preparation thereof |
-
2009
- 2009-08-17 CN CN2009101159940A patent/CN101628963B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781962A (en) * | 2004-12-03 | 2006-06-07 | 赵亚娟 | Method for producing polyurethane resin for synthetic leather |
| CN101381448A (en) * | 2008-10-14 | 2009-03-11 | 太仓市旭川树脂有限公司 | Polyurethane resin for water proof and breathable clothing leather |
| CN101486801A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density polyurethane micropore elastomer added with thermal foamable microsphere and preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101628963A (en) | 2010-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2344378C (en) | Improved cellular plastic material | |
| CN101628964B (en) | Bi-components for manufacturing polyurethane sole materials | |
| CN100569823C (en) | At the bottom of a kind of polyether type polyurethane shoes and preparation method thereof | |
| CN103483530B (en) | A kind of Polyether urethane shoe sole raw liquorbasic solution | |
| CN100572413C (en) | Polyester type ultra-low density polyurethane resin for shoes | |
| CN102329410B (en) | Preparation method of polyester and polyether mixed type polyurethane material with high fluidity | |
| CN101735597A (en) | Resin for polyurethane shoe with extremely-low density and high hardness and preparation method thereof | |
| CN101486801A (en) | Low density polyurethane micropore elastomer added with thermal foamable microsphere and preparation thereof | |
| CN101177473B (en) | Low-density timber-imitation polyurethane resin for shoes | |
| CN101429271B (en) | Polyether type resin for low-rigidity transparent anti-skidding shoes | |
| CN103570908A (en) | Polyurethane sole material raw liquid | |
| CN101628963B (en) | Bicomponent for manufacturing polyester polyurethane woodlike material | |
| CN102417588B (en) | Polyester polyurethane sole stoste and preparation method thereof | |
| CN107614615A (en) | Introduce the thermoplastic polyurethane for being available for Jiao Lian Wei Ge and the method for crosslinked foaming is carried out using it | |
| CN1171925C (en) | Preparation method of polyether polyarethane microporous elastic body | |
| CN101469052A (en) | Preparation of polyurethane buffering stop block for sedan car | |
| CN101503500A (en) | Resin for polyester type shoes | |
| CN103044898A (en) | Pore-forming agent for polyurethane elastomers and application of pore-forming agent | |
| CN106674494A (en) | Polyester polyol and anti-flooding polyurethane surface layer resin | |
| CN105085856A (en) | Polyurethane resin | |
| SU857152A1 (en) | Method of producing stiff porous polyurethan | |
| JP2000336136A (en) | Polyurethane binder and elastic paving member using the same |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: XUCHUAN CHEMICAL (KUNSHAN) CO., LTD. Free format text: FORMER OWNER: XUCHUAN CHEMICAL (SUZHOU) CO., LTD. Effective date: 20111124 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 215434 SUZHOU, JIANGSU PROVINCE TO: 215345 SUZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20111124 Address after: Xinle city Kunshan road 215345 Jiangsu Dianshan Lake Town No. 198 Patentee after: Asahikawa chemical (Kunshan) Co., Ltd. Address before: GCL Port Development Zone Road 215434 Jiangsu city of Taicang Province, No. 3 Patentee before: Xuchuan Chemical (Suzhou) Co., Ltd. |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110413 Termination date: 20130817 |