CN104193934A - Preparing method of polymer polyol used for environmental friendly polyurethane block flexible foam - Google Patents
Preparing method of polymer polyol used for environmental friendly polyurethane block flexible foam Download PDFInfo
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- CN104193934A CN104193934A CN201410253945.4A CN201410253945A CN104193934A CN 104193934 A CN104193934 A CN 104193934A CN 201410253945 A CN201410253945 A CN 201410253945A CN 104193934 A CN104193934 A CN 104193934A
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- polyether glycol
- trimeric cyanamide
- polymer polyol
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- polymer polyatomic
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a preparing method of environmental friendly polymer polyol and polyurethane flexible foam. The method includes preparing the polymer polyol and preparing flexible foam polyurethane blocks by utilization of the polymer polyol. The polymer polyol is advantageous in that: 1) the polymer polyol is free of styrene and acrylonitrile which are toxic and free of harm to human bodies and can be used next to the skin; 2) the cost of the polymer polyol is lower than the cost of polymer polyol manufactured by styrene and acrylonitrile; and 3) the burning oxygen index of the polymer polyol provided by the invention is little higher than that of the polymer polyol manufactured by the styrene and the acrylonitrile. The block flexible polyurethane foam is prepared from polyether polyol and the polymer polyol provided by the invention. The method is suitable to be used in manufacturing of environmental-friendly nontoxic and harmless block flexible foam plastic.
Description
Technical field
The invention belongs to polyurethane synthetic material field.Specifically, be a kind of environmentally friendly polymer polyatomic alcohol and flexible polyurethane foam preparation method.
Background technology
Flexible urethane foam is divided into substantially: high resilience flex foam, the large class of general block flex foam two.
High resilience flex foam production method is divided into two classes: the one, and adopt high-activity high molecular weight polyether polyol to add that various linking agent reacts and forms with polyisocyanates, the 2nd, adopting graft type polyethers is that polymer polyatomic alcohol reacts and forms with polyisocyanates.
General block flex foam, polyether glycol used functional group generally more than 2, hydroxyl value equivalent approximately 1000 left and right, conventionally with the trihydroxy-polyethers application of molecular weight 3000 at most.Adding polymer polyatomic alcohol to be equivalent to introduce mineral filler, is one of effective ways that improve flex foam compression load.
Conventionally, polymer polyatomic alcohol is that in the mode of radical polymerization, graft copolymerization forms in polyether glycol medium by olefinic monomer (vinylbenzene, vinyl cyanide etc.).It can improve rebound degree, load and the opening of high resilience flex foam and general block flex foam.
General block flex foam product application is extensive, such as lining and the U.S. chest cotton etc. of automobile, aero seat, furniture, clothes shoes.
Vinylbenzene, vinyl cyanide residual in polymer polyatomic alcohol are toxic substance, and the smell is awful, limited the application of polymer polyatomic alcohol.
Current, block foam is by polymer polyatomic alcohol making method only for the radical polymerization mode taking vinylbenzene, vinyl cyanide as monomer, and other method has no report.Domestic do not have patent open.
Summary of the invention
In order to discard vinylbenzene, the use of vinyl cyanide in the soft bubble urethane of bulk, the present invention proposes polymer polyatomic alcohol and flexible polyurethane foam preparation method.The method, by adopting trimeric cyanamide, the alternative vinylbenzene of urea and propylene fine, by polymer polyatomic alcohol synthesis step, solves the technical problem of flexible foamed urethane toxicological harmless.
The scheme that technical solution problem of the present invention adopts is:
Polymer polyatomic alcohol preparation:
Chemistry polycondensation method, taking trimeric cyanamide as polycondensation core, by trimeric cyanamide, urea, formaldehyde condensation polymer, and local grafting, is distributed to functional group more than 2, and hydroxyl value equivalent is 1000, in the trihydroxy-polyether glycol of molecular weight 3000, prepares polymer polyatomic alcohol.
Prepare flexible foamed polyurethane block body:
Polyether glycol is coordinated to synthetic block polyurathamc blocks with polymer polyatomic alcohol and auxiliary agent.
Concrete preparation process:
Polymer polyatomic alcohol preparation:
1), synthesize two kinds of functionality 3, hydroxyl value equivalent 1000, the polyether glycol of molecular weight 3000.
The first polyether glycol is: ethylene oxide content 10% ~ 20% end-blocking, and primary hydroxyl is higher than 60%, and hydroxyl value is 55 ~ 57mgKOH/g, obtains functionality 3, hydroxyl value equivalent 1000, the polyether glycol of molecular weight 3000.
The second polyether glycol is: ethylene oxide content 10% ~ 20% and propylene oxide blending polymerization, hydroxyl value is 55 ~ 57mgKOH/g, obtains functionality 3, hydroxyl value equivalent 1000, the polyether glycol of molecular weight 3000.
The synthetic initiator of polyether glycol selects glycerine, TriMethylolPropane(TMP), and polymerizing catalyst is selected potassium hydroxide, sodium hydroxide, and polymerization temperature is controlled at 80 ~ 120 DEG C, and polymerization time is 4 ~ 6 hours.
2), trimeric cyanamide methylolation, form polycondensation core:
A part of trimeric cyanamide is added to reactor, by formaldehyde adjusting pH value 7-9, add reactor, open to stir and heat up 75 DEG C, treat solution clarification, be incubated 1 hour, methylolation completes.PH regulator can be selected potassium hydroxide, sodium hydroxide solution or trolamine;
3), in trihydroxy-polyether glycol, disperse or local grafting trimeric cyanamide:
Two kinds of polyether glycols of synthesized are mixed in proportion, then add trimeric cyanamide methylolation liquid to mix, regulate pH value 4-6, open stirring intensification 80-90 DEG C, be incubated 1 hour, pH regulator is selected hydrochloric acid or phosphoric acid, ammonium phosphate;
4), trimeric cyanamide, urea, formaldehyde polycondensation again:
Dispersion grafting mixture is added to reactor, add water, methyl alcohol, alcohol solvent simultaneously, add remaining trimeric cyanamide, urea, formaldehyde according to the requirement of solid content, and regulation system pH value 6-8, open and stir intensification 80-160 DEG C, maintain 4 hours, deviate from water and solvent and finally make polymer polyatomic alcohol.
Block flexible polyurethane foam preparation:
Press mass fraction,
Raw material:
30 parts-70 parts of molecular weight 3000 polyether glycols,
30 parts-70 parts of polymer polyatomic alcohols;
Auxiliary agent:
0.5-1.5 parts of silicon foams stablizers,
0.3-1.5 parts of catalyzer,
2-6 parts of whipping agents,
TDI index 0.8---1.1.
Positively effect, the advantage of polymer polyatomic alcohol of the present invention: 1, not containing vinylbenzene, vinyl cyanide toxic substance, harmless can next to the skinly use.2, the polymer polyatomic alcohol cost that this polymer polyatomic alcohol is made of vinylbenzene, vinyl cyanide is low.3, burns oxygen index is a little more than the polymer polyatomic alcohol of making of vinylbenzene, vinyl cyanide.Manufacture block flexible polyurethane foam with polyether glycol and polymer polyatomic alcohol.Suitable method application of manufacturing as the block flex foam of environmentally friendly toxicological harmless.
Specific embodiments
Embodiment mono-:
Synthetic functionality 3, hydroxyl value equivalent 1000, the polyether glycol 1# of molecular weight 3000.
Autoclave adds glycerine, potassium hydroxide, nitrogen replacement 3 times, heat up 80 DEG C, add propylene oxide 80% ~ 90% polymerization, 80 ~ 120 DEG C of temperature, slaking is to constant pressure, continue to add oxyethane 10% ~ 20% polymerization, 80 ~ 120 DEG C of temperature, slaking is to constant pressure, the refining potassium ion of removing, obtain polyether glycol: ethylene oxide content 10% ~ 20% end-blocking, primary hydroxyl is higher than 60%, and hydroxyl value is 55 ~ 57mgKOH/g.
Embodiment bis-:
Synthetic functionality 3, hydroxyl value equivalent 1000, the polyether glycol 2# of molecular weight 3000.
Autoclave adds glycerine, potassium hydroxide, nitrogen replacement 3 times, heat up 80 DEG C, add propylene oxide 80% ~ 90%, oxyethane 10% ~ 20% mix monomer polymerization, 80 ~ 120 DEG C of temperature, slaking is to constant pressure, the refining potassium ion of removing, obtains polyether glycol: ethylene oxide content 10% ~ 20% and propylene oxide blending polymerization, hydroxyl value is 55 ~ 57mgKOH/g.
Embodiment tri-:
Trimeric cyanamide is added to reactor, and formaldehyde regulates pH value 7-9 to add reactor, opens to stir and heats up 75 DEG C, treats solution clarification, is incubated 1 hour, and methylolation completes.Add in proportion polyether glycol 1#, 2#, regulate pH value 4-6, intensification 80-90 DEG C, be incubated 1 hour, add remaining trimeric cyanamide, urea, formaldehyde according to the requirement of solid content, and regulation system pH value 6-8, open and stir intensification 80-160 DEG C, maintain 4 hours.Deviate from water and solvent and finally make polymer polyatomic alcohol.
General block flex foam is made:
Press mass fraction:
30 parts-70 parts of polyether glycols (molecular weight 3000),
30 parts-70 parts of example three made polymer polyatomic alcohols,
0.5-1.5 parts of silicon foams stablizers,
0.3-1.5 parts of catalyzer,
2-6 parts of whipping agents,
TDI index 0.8-1.1.
More than stir and pour foam box into and make block foam.
Block foam index:
Density: 20.5 kg/m
3
Resilience: 50.6%
Tensile strength: 8.4 kg/cm
2
Tear strength: 42.5 kg/cm
Compressive strength: 50.3kg/314cm
2.
Claims (2)
1. environmentally friendly polymer polyatomic alcohol and flexible polyurethane foam preparation method, is characterized in that:
Polymer polyatomic alcohol preparation:
Chemistry polycondensation method, taking trimeric cyanamide as polycondensation core, by trimeric cyanamide, urea, formaldehyde condensation polymer, and local grafting, is distributed to functional group more than 2, and hydroxyl value equivalent is 1000, in the trihydroxy-polyether glycol of molecular weight 3000, prepares polymer polyatomic alcohol;
Concrete preparation process:
(1), synthesize two kinds of functionality 3, hydroxyl value equivalent 1000, the polyether glycol of molecular weight 3000;
The first polyether glycol is: ethylene oxide content 10% ~ 20% end-blocking, and primary hydroxyl is higher than 60%, and hydroxyl value is 55 ~ 57mgKOH/g, obtains functionality 3, hydroxyl value equivalent 1000, the polyether glycol of molecular weight 3000;
The second polyether glycol is: ethylene oxide content 10% ~ 20% and propylene oxide blending polymerization, and hydroxyl value is 55 ~ 57mgKOH/g, obtains functionality 3, hydroxyl value equivalent 1000, the polyether glycol of molecular weight 3000;
The synthetic initiator of polyether glycol selects glycerine, TriMethylolPropane(TMP), and polymerizing catalyst is selected potassium hydroxide, sodium hydroxide, and polymerization temperature is controlled at 80 ~ 120 DEG C, and polymerization time is 4 ~ 6 hours;
(2), trimeric cyanamide methylolation, form polycondensation core:
A part of trimeric cyanamide is added to reactor, by formaldehyde adjusting pH value 7-9, add reactor, open to stir and heat up 75 DEG C, treat solution clarification, be incubated 1 hour, methylolation completes.PH regulator can be selected potassium hydroxide, sodium hydroxide solution or trolamine;
(3), in trihydroxy-polyether glycol, disperse or local grafting trimeric cyanamide:
Two kinds of polyether glycols of synthesized are mixed in proportion, then add trimeric cyanamide methylolation liquid to mix, regulate pH value 4-6, open stirring intensification 80-90 DEG C, be incubated 1 hour, pH regulator is selected hydrochloric acid or phosphoric acid, ammonium phosphate;
(4), trimeric cyanamide, urea, formaldehyde polycondensation again:
Dispersion grafting mixture is added to reactor, add water, methyl alcohol, alcohol solvent simultaneously, add remaining trimeric cyanamide, urea, formaldehyde according to the requirement of solid content, and regulation system pH value 6-8, open and stir intensification 80-160 DEG C, maintain 4 hours, deviate from water and solvent and finally make polymer polyatomic alcohol.
2. flexible polyurethane foam preparation: it is characterized in that:
Polyether glycol is coordinated to synthetic block polyurathamc blocks with polymer polyatomic alcohol and auxiliary agent;
Press mass fraction:
Raw material:
30 parts-70 parts of molecular weight 3000 polyether glycols,
30 parts-70 parts of polymer polyatomic alcohols;
Auxiliary agent:
0.5-1.5 parts of silicon foams stablizers,
0.3-1.5 parts of catalyzer,
2-6 parts of whipping agents,
TDI index 0.8-1.1.
Priority Applications (1)
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| CN201410253945.4A CN104193934B (en) | 2014-06-10 | 2014-06-10 | Environmentally friendly polymer polyatomic alcohol preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725796A (en) * | 2015-03-02 | 2015-06-24 | 上海雨竺实业有限公司 | Pure natural environment-friendly sponge |
| CN105968269A (en) * | 2016-07-12 | 2016-09-28 | 佳化化学科技发展（上海）有限公司 | Composition capable substituting styrene-acrylonitrile copolymerized POP (polymer polyol) |
| CN109400866A (en) * | 2018-09-29 | 2019-03-01 | 山东诺威新材料有限公司 | Flame retardant type sponge polyether polyol and preparation method thereof |
| CN110283287A (en) * | 2019-06-21 | 2019-09-27 | 航锦科技股份有限公司 | Flame-proof type polyalcohol polyalcohol industrialized production equipment and production method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812174A (en) * | 2010-04-01 | 2010-08-25 | 湖州创新聚氨酯科技有限公司 | Difficult-flammble polymer polyether glycol with high solid content and low viscosity as well as preparation method and application thereof |
| CN102250303A (en) * | 2010-05-21 | 2011-11-23 | 江苏绿源新材料有限公司 | Method for preparing polyurethane foam by using jatropha curcas oil-based soft polyether |
| CN103497557A (en) * | 2013-09-24 | 2014-01-08 | 北京工商大学 | Flame-retardant hard polyurethane foam |
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2014
- 2014-06-10 CN CN201410253945.4A patent/CN104193934B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812174A (en) * | 2010-04-01 | 2010-08-25 | 湖州创新聚氨酯科技有限公司 | Difficult-flammble polymer polyether glycol with high solid content and low viscosity as well as preparation method and application thereof |
| CN102250303A (en) * | 2010-05-21 | 2011-11-23 | 江苏绿源新材料有限公司 | Method for preparing polyurethane foam by using jatropha curcas oil-based soft polyether |
| CN103497557A (en) * | 2013-09-24 | 2014-01-08 | 北京工商大学 | Flame-retardant hard polyurethane foam |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725796A (en) * | 2015-03-02 | 2015-06-24 | 上海雨竺实业有限公司 | Pure natural environment-friendly sponge |
| CN105968269A (en) * | 2016-07-12 | 2016-09-28 | 佳化化学科技发展（上海）有限公司 | Composition capable substituting styrene-acrylonitrile copolymerized POP (polymer polyol) |
| US11261287B2 (en) | 2016-07-12 | 2022-03-01 | Jiahua Science & Technology Development (Shanghai) Ltd. | Composition capable of substituting use of styrene-acrylonitrile copolymer POP |
| CN109400866A (en) * | 2018-09-29 | 2019-03-01 | 山东诺威新材料有限公司 | Flame retardant type sponge polyether polyol and preparation method thereof |
| CN110283287A (en) * | 2019-06-21 | 2019-09-27 | 航锦科技股份有限公司 | Flame-proof type polyalcohol polyalcohol industrialized production equipment and production method |
| CN110283287B (en) * | 2019-06-21 | 2022-03-29 | 航锦科技股份有限公司 | Industrial production equipment and production method for flame-retardant polymer polyol |
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| CN104193934B (en) | 2016-04-06 |
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Address after: 125001 No. 1 chemical Street, Lianshan District, Liaoning, Huludao Patentee after: HANGJIN TECHNOLOGY CO.,LTD. Address before: 125001 No. 1 chemical Street, Lianshan District, Liaoning, Huludao Patentee before: FANGDA JINHUA CHEMICAL TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20220824 Address after: 125000 office building, building 1-113, chemical Street, Lianshan District, Huludao City, Liaoning Province Patentee after: Hangjin Jinxi Chlor Alkali Chemical Co.,Ltd. Address before: No. 1, Lianshan chemical Street, Huludao, Liaoning Province Patentee before: HANGJIN TECHNOLOGY CO.,LTD. |
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