CN1056386C - Synthesis of polymer polyalcohol by means of secondary grafting of starch-grafted polyether and its technological process - Google Patents
Synthesis of polymer polyalcohol by means of secondary grafting of starch-grafted polyether and its technological process Download PDFInfo
- Publication number
- CN1056386C CN1056386C CN95111076A CN95111076A CN1056386C CN 1056386 C CN1056386 C CN 1056386C CN 95111076 A CN95111076 A CN 95111076A CN 95111076 A CN95111076 A CN 95111076A CN 1056386 C CN1056386 C CN 1056386C
- Authority
- CN
- China
- Prior art keywords
- starch
- grafted polyether
- polyether
- grafting
- hour
- 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
- Graft Or Block Polymers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a dispersion liquid raw material used for synthesizing and manufacturing polyurethane foams or rubber, and a technology thereof. In the technology, toluene diisocyanate is used as a coupling agent for causing starch and polyether to carry out grafting reaction for manufacturing starch grafting polyether; the starch grafting polyether generates secondary grafting with styrene and (or) acrylonitrile under the action of initiating agents for synthesizing and manufacturing the polymer polyatomic alcohol of the present invention.
Description
The present invention relates to dispersion liquid raw material and manufacture craft thereof that a kind of synthetic making flexible PU foam or urethanes are used.
At present, reach the anti-tearing toughness of opening for the supporting capacity that improves polyurethane foam both at home and abroad, usually earlier polyethers is carried out modification, it is the organic dispersions of preparation feedback type, organic dispersions in the polyvalent alcohol of this modification has played the effect that improves the polyurethane foam bearing capacity, and the active end group of grafting or copolymerization can participate in and the effect of isocyanic ester on the organic dispersions, so in increase foam bearing capacity, not obvious other indexs that influences, the product good combination property.In addition, polyether segment on the organic dispersions and polyvalent alcohol have very big interaction, so can make organic dispersions evenly, stably be dispersed in the polyvalent alcohol, just can foam thereby need not that original foaming machine is done any change.The organic dispersions of this response type is representative with the polymer polyatomic alcohol, and it is to be formed by polyether grafting vinylbenzene and vinyl cyanide, and its grafting amount generally is no less than 20%.But, because the price of vinylbenzene, vinyl cyanide rises steadily in recent years, make polymer polyatomic alcohol dispersion liquid cost improve, limited applying of product.Therefore press for lower and the polymer polyatomic alcohol that performance is similar of a kind of cost of development.
Purpose of the present invention is exactly in order to address the above problem, and proposes a kind of secondary grafting of starch-grafted polyether synthesis of polymer polyalcohol and technology passed through, and this technology can significantly reduce vinylbenzene and vinyl cyanide consumption, and cost reduces, and product performance are constant.
Technical solution of the present invention:
A kind of by the secondary grafting of starch-grafted polyether synthesis of polymer polyalcohol, it is characterized in that it is that coupling agent makes starch-grafted polyether with starch and polyether grafting reaction by tolylene diisocyanate earlier, its structural formula is: the weight percent of its each composition consists of:
Starch-grafted polyether 74-95%
Vinylbenzene and (or) vinyl cyanide 4-25%
Initiator 0.5-1.2%
2, described by claim 1 by secondary grafting of starch-grafted polyether synthetic polymer polyatomic alcohol, it is characterized in that described initiator adopts Diisopropyl azodicarboxylate.
3, a kind of by secondary grafting of starch-grafted polyether polymer polyatomic alcohol method, it is characterized in that:
A. starch is added in the polyethers and stir, drip the tolylene diisocyanate coupling agent, drip reacting temperature is controlled at 20-50 ℃, and the dropping time was controlled at 0.5-1 hour, dropwised and was warming up to 100-115 ℃, reacted 1-2 hour, promptly made starch-grafted polyether;
B. in the above-mentioned starch-grafted polyether that makes, then add initiator, drip styrene and/or vinyl cyanide again, the dropping time was controlled at 1-2 hour, temperature of reaction is controlled at 100-115 ℃, reacted again 1-2 hour, under this temperature, vacuumize dehydration 1.5-2 hour at last, promptly make polymer polyatomic alcohol of the present invention.
A kind of by secondary grafting of starch-grafted polyether polymer polyatomic alcohol technology, it is characterized in that:
A. starch is added in the polyethers and stir, drip the tolylene diisocyanate coupling agent, drip reacting temperature is controlled at 20-50 ℃, and the dropping time was controlled at 0.5-1 hour, dropwised and was warming up to 100-115 ℃, reacted 1-2 hour, promptly made starch-grafted polyether;
B. in the above-mentioned starch-grafted polyether that makes, then add initiator, again drip styrene and (or) vinyl cyanide, the dropping time was controlled at 1-2 hour, temperature of reaction still is controlled at 100-115 ℃, reacted again 1-2 hour, under this temperature, vacuumize dehydration 1.5-2 hour at last, promptly make polymer polyatomic alcohol of the present invention.
The present invention has found to realize the approach of starch and polyethers chemical graft first, is main grafting raw material with starch, with its graft polyether, and graft phenylethene, vinyl cyanide again, secondary grafting is reflected under installing and carries out, and is simple for process.The present invention then compares with existing polymer polyatomic alcohol because the cheap starch of employing is main grafting raw material, and its vinylbenzene, vinyl cyanide consumption can significantly reduce, thereby have reduced the cost of polymer polyatomic alcohol of the present invention, the also corresponding minimizing of environmental pollution.Polymer polyatomic alcohol of the present invention promptly can be used as the raw material of synthetic high resilience cold-cured polyurethane foams plastics, also can be used as the raw material of synthetic high-mechanic urethane foam, equally also can be used as the raw material of synthesizing polyurethane rubber or polyurethane binder, can improve the foamy percentage of open area, improve the foamy processing characteristics, the bearing capacity of its goods is significantly increased, and other performance of goods is unaffected, and the product over-all properties is superior.
Embodiment (is example to produce 100 gram polymer polyatomic alcohols):
Adding 80 gram N-5613 polyethers in reaction vessel (Mn=3000, f=3), also available N-2801 polyethers etc.Add dried starch 10 grams (generally being not less than 300 orders) then, stir and be warming up to 50 ℃, drip 0.6 gram tolylene diisocyanate (TDI80/20) coupling agent, 0.5 hour dropping time than fine grain size.Dropwise and be warming up to 105 ℃, react and promptly made to starch-grafted polyethers in 1 hour, its chemical equation is:
Then in reaction vessel, add 0.6 gram initiator, initiator preferably adopts Diisopropyl azodicarboxylate, Dropwise 5 gram vinylbenzene and 5 restrains vinyl cyanide then, the dropping time is 1.5 hours, reaction is 1.5 hours under 105 ℃ of temperature, vacuumized under 105 ℃ 1.5 hours at last, products therefrom is polymer polyatomic alcohol of the present invention, and its chemical equation is:
The index of the above-mentioned polymer polyatomic alcohol that makes is:
Hydroxyl value (mgkoH/g): 50
Moisture content (%)＜0.2%
Viscosity (Pa.S) 240000
(centipoise) (2400)
This polymer polyatomic alcohol is suitable for the raw material as preparation high-mechanic polyurethane foam.
If adopt Tianjin 330 high activity polyethers (its index is for Mn=4700, the f=3) polymer polyatomic alcohol of the present invention that makes by above-mentioned twice graft process with starch:
Hydroxyl value (mgkoH/g): 28
Moisture content (%)＜0.2%
Viscosity (Pa.S) 240000
(centipoise) (2400)
This polymer polyatomic alcohol is suitable for the raw material as the preparation high resilience polyurethane foam.
The present invention is according to existing hydroxyl in the starch molecule, and also there is the hydroxyl of certain content in polyethers, and utilizes isocyanic ester and hydroxyl that the principle of chemical reaction easily takes place, and has realized the graft reaction between starch and the polyethers.Here, the isocyanide ester plays a function served as bridge that links starch and polyether reactant.If starch directly is distributed in the polyethers, its synthetic polymer polyatomic alcohol less stable, except that amount of starch by the physical adsorption, other will cause unstable bad phenomenon such as layering, influence the performance of its quality and synthetic products.Therefore, adopt secondary grafting of starch-grafted polyether vinylbenzene, vinyl cyanide synthesis of polymer polyalcohol, vinylbenzene, vinyl cyanide consumption are reduced more than one times at least, cost is reduced, simultaneously do not influence Products Quality and performance, aspect load-carrying properties, also improve to some extent.
Claims (3)
1, a kind of by secondary grafting of starch-grafted polyether synthetic polymer polyatomic alcohol, it is characterized in that it is that coupling agent makes starch-grafted polyether with starch and polyether grafting reaction by tolylene diisocyanate earlier, its structural formula is:
The weight percent of its each composition consists of:
Polyethers 69-90%
Starch 5-30%
Tolylene diisocyanate 0.4-2.0%
Again starch-grafted polyether is made polymer polyatomic alcohol of the present invention with vinylbenzene and/or vinyl cyanide secondary grafting are synthetic under the initiator effect, its molecular structural formula is:
The weight percent of its each composition consists of:
Starch-grafted polyether 74-95%
Vinylbenzene and (or) vinyl cyanide 4-25%
Initiator 0.5-1.2%
2, described by claim 1 by secondary grafting of starch-grafted polyether synthetic polymer polyatomic alcohol, it is characterized in that described initiator adopts Diisopropyl azodicarboxylate.
3, a kind of by secondary grafting of starch-grafted polyether polymer polyatomic alcohol method, it is characterized in that:
A. starch is added in the polyethers and stir, drip the tolylene diisocyanate coupling agent, drip reacting temperature is controlled at 20-50 ℃, and the dropping time was controlled at 0.5-1 hour, dropwised and was warming up to 100-115 ℃, reacted 1-2 hour, and first makes starch-grafted polyether;
B. in the above-mentioned starch-grafted polyether that makes, then add initiator, drip styrene and/or vinyl cyanide again, the dropping time was controlled at 1-2 hour, temperature of reaction is controlled at 100-115 ℃, reacted again 1-2 hour, under this temperature, vacuumize dehydration 1.5-2 hour at last, promptly make polymer polyatomic alcohol of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111076A CN1056386C (en) | 1995-06-16 | 1995-06-16 | Synthesis of polymer polyalcohol by means of secondary grafting of starch-grafted polyether and its technological process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111076A CN1056386C (en) | 1995-06-16 | 1995-06-16 | Synthesis of polymer polyalcohol by means of secondary grafting of starch-grafted polyether and its technological process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1128274A CN1128274A (en) | 1996-08-07 |
| CN1056386C true CN1056386C (en) | 2000-09-13 |
Family
ID=5078394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111076A Expired - Fee Related CN1056386C (en) | 1995-06-16 | 1995-06-16 | Synthesis of polymer polyalcohol by means of secondary grafting of starch-grafted polyether and its technological process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1056386C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180137A (en) * | 2010-10-27 | 2013-06-26 | 罗盖特公司 | Method for producing a multilayer structure comprising an adhesive composition based on an amylaceous material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210053B (en) * | 2006-12-28 | 2010-07-07 | 中国科学院化学研究所 | Amphiphilic starch derivative fine particles and preparing method thereof |
| KR101534880B1 (en) * | 2007-07-12 | 2015-07-07 | 바스프 에스이 | Nitrocellulose based dispersant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0221412A2 (en) * | 1985-10-28 | 1987-05-13 | BASF Corporation | Process for the preparation of graft polymer dispersions and flame-retardant polyurethane foams |
| EP0502480A2 (en) * | 1991-03-06 | 1992-09-09 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin compositions |
-
1995
- 1995-06-16 CN CN95111076A patent/CN1056386C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0221412A2 (en) * | 1985-10-28 | 1987-05-13 | BASF Corporation | Process for the preparation of graft polymer dispersions and flame-retardant polyurethane foams |
| EP0502480A2 (en) * | 1991-03-06 | 1992-09-09 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180137A (en) * | 2010-10-27 | 2013-06-26 | 罗盖特公司 | Method for producing a multilayer structure comprising an adhesive composition based on an amylaceous material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1128274A (en) | 1996-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100484576B1 (en) | Polyether polyurethane | |
| CN1069654C (en) | Continuous process for preparation of highly stable, finely divided, low viscosity polymer polyols of small average particle size | |
| CN109438653A (en) | A kind of bion thermoplastic polyurethane elastomer and preparation method thereof | |
| US4403083A (en) | Preparation of solid polyurethane particles | |
| CN101942071B (en) | Polyurethane resin used for sofa leather and preparation process thereof | |
| Pavier et al. | Oxypropylation of sugar beet pulp. 1. Optimisation of the reaction | |
| JP2002508417A5 (en) | ||
| JPS58108219A (en) | Manufacture of crosslinked hydrophilic foamed body | |
| CN1056386C (en) | Synthesis of polymer polyalcohol by means of secondary grafting of starch-grafted polyether and its technological process | |
| CN100404576C (en) | Prepn process of nanometer starch crystal modified water-base polyurethane | |
| CN1144811A (en) | Low-viscosity polymeric polyols, process for their preparation and their use for manufacture of polyurethane foams | |
| US4169922A (en) | Rigid polyurethane foam-forming compositions | |
| CN110841702B (en) | Preparation method of catalyst for synthesizing aromatic nitrile and synthesis method of aromatic nitrile | |
| CN102272188B (en) | A foamed isocyanate-based polymer, a mix and process for production thereof | |
| CN111647109A (en) | Modified starch fluid loss additive and preparation method thereof | |
| CN101343347A (en) | Method for synthesis of high solid content polymer polyol macromer with vegetable oil and uses thereof | |
| KR970015566A (en) | Polyisocyanate based on diphenylmethane diisocyanate containing allophanate group and blocked isocyanate group | |
| Tabaght et al. | Synthesis, characterization, and biodegradation studies of new cellulose-based polymers | |
| IE903558A1 (en) | Shaped articles of substances containing wood or cellulose¹and processes for their production | |
| EP0318242A3 (en) | Polymer polyols with high solids content | |
| EP1196470A1 (en) | Polyisocyanate compositions for fast cure | |
| CN112920369A (en) | Self-antibacterial lactic acid-based waterborne polyurethane, preparation method and emulsion thereof | |
| CA2027354C (en) | Polyisocyanate compositions and their use in the preparation of flexible polyurethane foams | |
| KR960041223A (en) | Process for preparing continuous foamable polyurethane modified polyisocyanurate foam | |
| GB2260138A (en) | Biodegradable composite material and process of producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: PATENTEE; FROM: CHEN SU TO: NANJING CHEMICAL UNIV. |
|
| CP03 | Change of name, title or address |
Address after: 210009, 5 new exemplary Road, Jiangsu, Nanjing Patentee after: Nanjing Chemical Univ. Address before: Outside the East Central wells village of Nanjing city in Jiangsu province 210028 (nansu dormitory) building 14 Room 401 Patentee before: Chen Su |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |