CN102167791B - Reaction type flame retardant for soft polyurethane foam and application - Google Patents
Reaction type flame retardant for soft polyurethane foam and application Download PDFInfo
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- CN102167791B CN102167791B CN201110046393A CN201110046393A CN102167791B CN 102167791 B CN102167791 B CN 102167791B CN 201110046393 A CN201110046393 A CN 201110046393A CN 201110046393 A CN201110046393 A CN 201110046393A CN 102167791 B CN102167791 B CN 102167791B
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- flame retardant
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- phosphorous
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Abstract
The invention discloses a reaction type flame retardant for soft polyurethane foam and an application, belonging to the technical field of the flame retardants. The reaction type flame retardant contains three components, namely a phosphorus-containing polyhydroxy compound, a halogen-containing polylol and a chain extender with two degrees of functionality. When the flame retardant is in use, the reaction type flame retardant can be directly added into polyether polylol and is good in compatibility with the polyether polylol, and the precipitation can be avoided. The polyurethane foam prepared by the reaction type flame retardant is lasting in flame retarding effect and further has the characteristics of low VOC (volatile organic compounds) and low atomization, the flame retarding effect can not be reduced after aging, and adverse impacts on physical properties of the foam can be avoided. The soft foam using the flame retardant has excellent flame laminating performance and great peeling strength, and is suitable for being used as an interior trimming material for automobiles and airplanes.
Description
Technical field
The present invention relates to a kind of reactive flame retardant and in polyurethane soft foamed plastics, use, belong to the fire retardant technical field.
Background technology
Flexible polyurethane foams has light weight softness, insulation, excellent specific property such as ventilative, is widely used in a plurality of industries such as aircraft, automobile, steamer, furniture.Yet the urethane foam base material existing very easily fire burns, drippage, flame spread rapidly, the extremely difficult defective of the aspect such as putting out.The most frequently used method that addresses this problem is added fire retardant exactly in the polyurethane foam process, have many fire retardants that relate to be disclosed with the document that improves the urethane foam physical properties.For example; U.S. Pat P6855741 discloses a kind of improved flexible urethane foam; Its fire retardant adopts phthalic acid alkyl benzyl ester and SULPHOSUCCINIC ACID ESTER, and water is as whipping agent, in order to improve the foam deterioration of the physicals brought to foam of water; Through in porous plastics, add softening agent for example phthalic ester or SULPHOSUCCINIC ACID ESTER urethane foam is softened, also add linking agent simultaneously and improve the foamy physicals.
The technology of this use additive flame retardant has following shortcoming: 1.. and in the urethane foam use, transport phenomena may take place in fire retardant, causes the reduction of flame retardant effect; The small molecules fire retardant that migration is come out can make the mist value and the VOC of soft bubble defective, and being applied to automobile is especially to require to have these characteristics.2. additive flame retardant is bigger to the mechanical property and the use properties influence of urethane foam, shows that mainly stretching and rebound performance have decline significantly.Though use softening agent can temporarily improve the foamy performance, but softening agent has toxicity, has been limited gradually to use.And softening agent is moved out easily, will cause foamy mist value and VOC defective.
Summary of the invention
The object of the invention provides a kind of good flame retardation effect, the ground fog value that is difficult for moving out again and fire retardant and the application thereof of low VOC, and in fire-retardant, can keep the physical and mechanical properties of urethane foam.
Based on above consideration; The invention provides on the polyurethane foam molecular chain; The method of introducing ignition-proof element phosphorus and halogen according to suitable ratio simultaneously reaches a kind of fire retardant of flame retardant effect preferably, adds certain polyhydric material simultaneously, improves the foamy physical and mechanical properties.
Reactive flame retardant provided by the invention contains three kinds of components: a kind of phosphorous polyol, the chainextender of a kind of halogenous polyvalent alcohol and a kind of 2 functionality.
The mass content of phosphorous polyol is 30-50% in the fire retardant of the present invention, and the mass content of halogenous polyvalent alcohol is 30-50%, and the mass content of the chainextender of 2 functionality is 10-30%.Compsn normally mixes under 30～90 ℃ the condition and makes.
Phosphorous polyol in the fire retardant according to the invention can be phosphorous acid esters, and molecular formula is P (OR
1OH)
3, also can be phosphoric acid ester, molecular formula is O=P (OR
2OH)
3, R wherein
1And R
2Saturated alkylene for 2-3 carbon atom.In the above-mentioned phosphorous polyol, phosphorous acid esters are preferred especially.Phosphorous polyol of the present invention also can be the phosphorated polyol oligomer.
Halogenous polyvalent alcohol in the fire retardant according to the invention can be aromatic series or aliphatics halogenated alcohols or its mixture, also can be one or more of halides of aliphatics tetramethylolmethane.
2 functionality chainextenders in the fire retardant according to the invention can be low molecular weight diol, like terepthaloyl moietie, and 1,4-butyleneglycols etc. also can be polyether polyol, the polyester polyol of lower molecular weight.For the object of the invention, polyester polyol is preferred especially.Suitably the representative example of polyester polyol comprises phthalic acid ester group, ethylene glycol and glycol ether base aromatic series and aliphatic polyester polyols, is preferably the phthalate polyester polyol.
Reactive flame retardant of the present invention can directly add in the polyether glycol when using and the consistency of polyether glycol good, can not separate out.
The method of manufacture of soft flame retardant polyurethane foamed plastics provided by the invention is the general water foaming casting technology that adopts.The preparation method is summarized as follows; The dipropylene glycol solution (A33) of the triethylenediamine of the mass concentration 33% of two (2-dimethyl aminoethyl) ethers (A1) of adding polyether glycol 100 parts of (molecular weight of hydroxyl value 56 is 3000 3 functionality polyether glycols), fire retardant 3-12 parts, 3.0 parts in water, 0.05-0.08 part and 0.09-0.12 part, 1.5 parts foam stabilizer in first container, and stirring 10s mixes it.In another container, the tolylene diisocyanate of the required quality of weighing (TDI80/20).Inject first container to the organotin catalysts stannous octoate (T-9) of 0.2-0.3 part; Stirred 10 seconds; Then the TDI that weighs up (index is 110) is joined in the mixture, and then continue to stir 10 seconds, be placed into the fluid mixture after leaving standstill in the mould rapidly; After foam stops growing, with foam as for ventilation slaking 24h.The appearance piece that can be cut into regulation after the foam slaking is accomplished is tested.
The flexible PU foam that reactive flame retardant of the present invention makes, flame retardant effect is lasting, and has the characteristics of low VOC and low atomizing, and the flame retardant effect after wearing out can not reduce, and the foamy physicals is not had negative impact.More particularly the place is, uses the soft bubble of this fire retardant to have good flame composite performance, and stripping strength is big, is particularly suitable for automobile, airplane industry use.
Embodiment
Foaming and detected result below in conjunction with flexible PU foam further specify the present invention, rather than limit scope of the present invention.
In common foaming process, in first cup, add polyether glycol, fire retardant, water, amines catalyst and silicone oil foam stabilizer.In another cup, the tolylene diisocyanate of weighing (TDI80/20).Stir material in first cup 10 seconds; Inject organotin catalysts wherein, restir 10 seconds joins TDI in the mixture then; And then continue to stir 10 seconds; Fluid mixture after leaving standstill is placed into rapidly in the square chest of 50cm, and measurement begins rise time, stand-by time etc.After foam stops to rise, foam is cut into the appearance piece of regulation after as for ventilation slaking 24h and tests.
Below table 1 provide a kind of according to the present invention the prescription (consumption of each material is a mass ratio in the table) of preferred especially polyurethane soft foamed plastics.
Table 1
| TMN3050 (hydroxyl value 56, molecular weight 3000) | 100 |
| Water | 3.0 |
| Fire retardant of the present invention | 3-12 |
| DC5950 (foam stabilizer) | 1.5 |
| A1 | 0.05～0.08 |
| A33 | 0.09～0.12 |
| T9 | 0.2～0.3 |
| The TDI index | 110 |
Testing method:
The mensuration of 1 rebound performance GB/T6670-2008 flexible urethane foam rebound performance
2 press the mensuration (pressing the method for falling into) that falls into performance GB/T10807-2006 flexible foam polymeric materials hardness
The combustioncharacteristics of 3 flame retardant properties GB 8410-2006 automotive interior materials, horizontal burning test is tested (specimen size is 355mm*100mm*10mm, and first graticule is apart from free end 38mm, and second graticule is apart from free end 292mm) by FMVSS 302 standards.
The soft composite plastics material stripping test of 4 stripping strength GB8808-1988 method
Change the composition and the consumption of fire retardant of the present invention, carry out each item test after foaming respectively according to the prescription of table 1.The composition of fire retardant is seen table 2 among the embodiment, and the result of the test of foaming properties sees table 3.
The composition of table 2 fire retardant
Annotate: Weston430 is three (DPG) phosphorous acid ester
OP550, OP560 are the low polyphosphate divalent alcohol
PS3152, PS1752 are polyester polyol
TD400 is a polyether glycol
Gained foamy performance under table 3 different flame retardant composition and the consumption
Can know that by table 3 use the flexible PU foam flame retardant effect of the used fire retardant preparation of the present invention obvious, physical and mechanical properties does not have influence basically; It is worthy of note especially; After using foam and the fabric of fire retardant of the present invention compound, compound fastness is strong, and stripping strength is high.Fire retardant of the present invention is a reactive flame retardant, and foaming back fire retardant is attached in the foamy structure, can not separate out, and low atomizing, low VCO is fit to automobile industry and uses.
Claims (5)
1. a reactive flame retardant that is used for flexible PU foam is characterized in that, contains three kinds of components: a kind of phosphorous polyol, the chainextender of a kind of halogenous polyvalent alcohol and a kind of 2 functionality;
The mass content of phosphorous polyol is 30-50%, and the mass content of halogenous polyvalent alcohol is 30-50%, and the mass content of the chainextender of 2 functionality is 10-30%;
Phosphorous polyol is phosphorous acid esters, phosphoric acid ester or phosphorated polyol oligomer, and the phosphorous acid esters molecular formula is P (OR
1OH)
3, the phosphoric acid ester molecular formula is O=P (OR
2OH)
3, R wherein
1And R
2Saturated alkylene for 2-3 carbon atom; Halogenous polyvalent alcohol is aromatic series or aliphatics halohydrin or its mixture, or one or more of the halides of aliphatics tetramethylolmethane; 2 functionality chainextenders are low molecular weight diol or polyester polyol.
2. according to the reactive flame retardant of claim 1, it is characterized in that phosphorous polyol is phosphorous acid esters.
3. according to the reactive flame retardant of claim 1, it is characterized in that 2 functionality chainextenders are polyester polyols.
4. utilize the reactive flame retardant of claim 1 to prepare the method for soft flame retardant polyurethane foamed plastics; It is characterized in that; Adopt water foaming casting technology; May further comprise the steps: the dipropylene glycol solution of 33% of two (2-dimethyl aminoethyl) ethers of 100 parts of polyether glycols of adding, fire retardant 3-12 part, 3.0 parts in water, 0.05-0.08 part and 0.09-0.12 part triethylenediamine, 1.5 parts foam stabilizer in first container; And stir 10s it is mixed, wherein polyether glycol is that the molecular weight of hydroxyl value 56 is 3000 3 functionality polyether glycols; In another container, the tolylene diisocyanate TDI80/20 of the required quality of weighing injects first container to the organotin catalysts stannous octoate of 0.2-0.3 part; Stirred 10 seconds; Be that 110 TDI joins in the mixture with the index that weighs up then, and then continue to stir 10 seconds, be placed into the fluid mixture after leaving standstill in the mould rapidly; After foam stops growing, foam is placed ventilation slaking 24h.
5. a reactive flame retardant that is used for flexible PU foam is characterized in that, its mass percent consists of: low polyphosphate divalent alcohol OP550 30%, tribromoneoamyl alcohol 40%, polyether glycol TD400 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110046393A CN102167791B (en) | 2011-02-25 | 2011-02-25 | Reaction type flame retardant for soft polyurethane foam and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110046393A CN102167791B (en) | 2011-02-25 | 2011-02-25 | Reaction type flame retardant for soft polyurethane foam and application |
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| Publication Number | Publication Date |
|---|---|
| CN102167791A CN102167791A (en) | 2011-08-31 |
| CN102167791B true CN102167791B (en) | 2012-08-29 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2931779B1 (en) * | 2012-12-14 | 2017-08-30 | Dow Global Technologies LLC | Flame retardant foam formulations |
| CN103046379B (en) * | 2012-12-17 | 2015-09-09 | 浙江理工大学 | Flame-retardant modified Aqueous Polyurethane Coating Agent of halogen-free phosphonate and preparation method thereof |
| KR101610460B1 (en) * | 2014-03-21 | 2016-04-07 | 현대자동차주식회사 | Flame retarded slabstock polyurethane foam composition for flame Lamination |
| CN104672427B (en) * | 2014-12-31 | 2018-02-13 | 上海馨源新材料科技有限公司 | Soft bubble of a kind of high hardness polyurethane for automotive upholstery and preparation method thereof |
| CN104558492B (en) * | 2014-12-31 | 2017-06-16 | 上海馨源新材料科技有限公司 | A kind of automobile-used polyurethane interior trim foam of low smell high fire-retardance and preparation method thereof |
| CN105199096A (en) * | 2015-11-11 | 2015-12-30 | 江苏钟山化工有限公司 | Preparation and application of nitrogen and phosphorus structured flame-retardant polyether polyol |
| CN105524248B (en) * | 2015-12-18 | 2018-12-04 | 山东蓝星东大化工有限责任公司 | Car door inner sidewall polyether combined material and preparation method thereof |
| CN106496505A (en) * | 2016-10-27 | 2017-03-15 | 湖北科技学院 | A kind of phosphorus nitrogen cooperative flame retardant flexible polyurethane foam |
| CN107116876B (en) * | 2017-04-19 | 2019-05-24 | 杭州湘隽阻燃科技有限公司 | A kind of flame retardant automotive interior trim composite material and preparation method thereof |
| CN108383973B (en) * | 2018-02-12 | 2020-12-22 | 吴艳飞 | Full-water foaming spraying soft flame-retardant polyurethane thermal insulation material and preparation method thereof |
| CN116425938A (en) * | 2023-03-23 | 2023-07-14 | 江苏米尔化工科技有限公司 | Flame-retardant polyurethane soft foam with excellent mechanical properties and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN1649950A (en) * | 2002-05-06 | 2005-08-03 | 帕布服务公司 | Blends of tetrahalophthalate esters and phosphorus containing flame retardants for polyurethane compositions |
| CN1965009A (en) * | 2004-06-10 | 2007-05-16 | 溴化物有限公司 | Scorch prevention in flexible polyurethane foams |
| CN101278001A (en) * | 2005-09-16 | 2008-10-01 | 西巴特殊化学品控股有限公司 | Polyurethane flame retardant compositions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073368A1 (en) * | 1999-06-01 | 2000-12-07 | Solutia Inc. | Composition for use in flexible polyurethane foams |
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2011
- 2011-02-25 CN CN201110046393A patent/CN102167791B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1649950A (en) * | 2002-05-06 | 2005-08-03 | 帕布服务公司 | Blends of tetrahalophthalate esters and phosphorus containing flame retardants for polyurethane compositions |
| CN1965009A (en) * | 2004-06-10 | 2007-05-16 | 溴化物有限公司 | Scorch prevention in flexible polyurethane foams |
| CN101278001A (en) * | 2005-09-16 | 2008-10-01 | 西巴特殊化学品控股有限公司 | Polyurethane flame retardant compositions |
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| CN102167791A (en) | 2011-08-31 |
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Denomination of invention: Reaction type flame retardant for soft polyurethane foam and application Effective date of registration: 20150728 Granted publication date: 20120829 Pledgee: Beijing first financing Company limited by guarantee Pledgor: Beijing Novelite Co., Ltd. Registration number: 2015990000607 |
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Date of cancellation: 20150902 Granted publication date: 20120829 Pledgee: Beijing first financing Company limited by guarantee Pledgor: Beijing Novelite Co., Ltd. Registration number: 2015990000607 |
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Granted publication date: 20120829 Termination date: 20200225 |