CN105219038A - A kind of beta-cyclodextrin is the expandable flame retardant thermoplastic polyether ester elastomer in charcoal source and preparation method thereof - Google Patents
A kind of beta-cyclodextrin is the expandable flame retardant thermoplastic polyether ester elastomer in charcoal source and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of beta-cyclodextrin is the expandable flame retardant thermoplastic polyether ester elastomer in charcoal source and preparation method thereof, belongs to field of polymer composite material, relates to the special thermoplastic polyether ester elastomer matrix material of a kind of Novel cable.Comprise: thermoplastic polyether ester elastomer, Intumescent Retardant System and fire retarding synergist, according to quality proportioning: thermoplastic polyether ester elastomer 100 parts, phosphorus nitrogen Intumescent Retardant System 20 ~ 40 parts, fire retarding synergist 0.5 ~ 5 part; Wherein, described Intumescent Retardant System mixes by containing acid source, source of the gas and charcoal source component.Acid source and source of the gas are the combination of one or more in organic phosphonateflame retardant and trimeric cyanamide based flame retardant, and charcoal source is beta-cyclodextrin.The present invention by selecting specific expanding fire retardant, and using the beta-cyclodextrin of environmental protection as charcoal source, carries out flame-retardant modified to thermoplastic polyether ester elastomer, the flame retardant thermoplastic polyether ester elastomer obtained, not halogen-containing, Environmental Safety, flame retardant properties reaches UL94V-0 level.
Description
Technical field
The present invention relates to technical field of polymer materials, being specifically related to a kind of beta-cyclodextrin is charcoal source expandable flame retardant thermoplastic polyether ester elastomer and preparation method thereof.
Background technology
Thermoplastic polyether ester elastomer has snappiness, snappiness, the reversibility of rubber, thermoplastics processing method can be utilized again processing modified, or replace conventional rubber at present in some fields.But the thermoplastic polyether ester elastomer of conventional mixture is inflammable and have molten drop, limits the application of thermoplastic polyether ester elastomer, therefore need to carry out flame-retardant modified to it.
Current commercial flame retardant thermoplastic polyether ester elastomer is mainly through adding bromide fire retardant modification, but bromide fire retardant generation when burning jeopardizes the mankind and environmental safety dioxin, causes part bromide fire retardant be prohibited gradually and replace.Expansion type flame retardant is with phosphorus, nitrogen for main component, and not halogen-containing, contain acid source, source of the gas and charcoal source, be a kind of BACN of fast development simultaneously.But meet the requirements of flame retardant properties, expanding fire retardant addition is higher, efficient and stable char-forming agent, to raising expansion type flame retardant flame retarding efficiency, reduces addition significant.
Summary of the invention
In view of the above problems, the object of this invention is to provide a kind of environment friendly non-halogen expandable flame retardant thermoplastic polyether ester elastomer; Another object of the present invention is to provide above-mentioned halogen-free expanded flame-retardant thermoplastic polyether ester elastomer preparation method.Concrete technical scheme is as follows:
Beta-cyclodextrin is the expandable flame retardant thermoplastic polyether ester elastomer in charcoal source, and according to the mass fraction, its material component comprises:
Wherein, described thermoplastic polyether ester elastomer (TPEE) is the line-type block polymer that a class contains the hard section of polybutylene terephthalate and soft section of aliphatic polyether; Described phosphorus nitrogen Intumescent Retardant System is mixed by acid source, source of the gas and charcoal source component; Described acid source and source of the gas are respectively a kind of in organic phosphonateflame retardant and trimeric cyanamide based flame retardant or both combinations, and described charcoal source is beta-cyclodextrin.
The relative molecular mass of described polyester elastomer is 30,000 ~ 60,000g/mol, and fusing point is 170 ~ 195 DEG C, and shore hardness is 30 ~ 45D.
Described organic hypophosphite fire retardant is the Exolit series organic secondary phosphine acid salt that Clariant is produced, and is selected from the one in OP935, OP1240, OP1314.
Described trimeric cyanamide based flame retardant is one or more in trimeric cyanamide (MC), melamine polyphosphate (MPP), melamine cyanurate (MCA).
As the described beta-cyclodextrin in charcoal source without secondary treatment.
Described fire retarding synergist is anti-dripping agent, is selected from one or both in organic nano imvite (OMMT), polydimethylsiloxane (PDMS).
Described oxidation inhibitor is one or both in irgasfos 168 and antioxidant 1010.
Above-mentioned arbitrary described method for preparing polyether ester elastomer, comprises the steps:
(1) take raw material according to above-mentioned mass fraction, dry stand-by;
(2) thermoplastic polyether ester elastomer, fire retarding synergist and oxidation inhibitor that step (1) obtains are added high-speed mixer and mixing even;
(3) acid source step (1) obtained, source of the gas and three, charcoal source component add in high mixer, mix, are re-dubbed Intumescent Retardant System;
(4) mixture of step (2) gained is added in Banbury mixer, controlled working temperature is 185 ~ 205 DEG C, rotating speed is 90 ~ 120 revs/min, adds the Intumescent Retardant System of step (3) gained, continue banburying blended after material melts is complete;
(5) product of step (4) is added Single screw extrusion dicing machine fast, controlled working temperature is 135 ~ 160 DEG C, extruding pelletization, obtains the expandable flame retardant thermoplastic polyether ester elastomer that described beta-cyclodextrin is charcoal source.
Advantage of the present invention and beneficial effect as follows: utilize the composite phosphor nitrogen combustion inhibitor of environmental protection char-forming agent beta-cyclodextrin, composition Intumescent Retardant System, carry out flame-retardant modified to thermoplastic polyether ester elastomer.The flame retardant thermoplastic polyether ester elastomer obtained is not halogen-containing, Environmental Safety, and flame retardant properties reaches UL94V-0 level.
Embodiment
Below in conjunction with example, the present invention will be further described in detail, but be not limited to these examples, and the slip-stick artist in this field can carry out nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
The beta-cyclodextrin of following embodiment is the expandable flame retardant thermoplastic polyether ester elastomer in charcoal source, is prepared from by following working method:
(1) weigh thermoplastic polyether ester elastomer (TPEE), melamine series fire retardant (MPP/MCA/MC), oxidation inhibitor (168/1010) and beta-cyclodextrin according to proportioning, dry 12h in 95 DEG C;
(2) by thermoplastic polyether ester elastomer (TPEE), fire retarding synergist (OMMT/PTFE) and oxidation inhibitor (168/1010) according to proportioning in high mixer with the rotating speed high-speed mixing 5-10min of 800r/min;
(3) acid source (OP935/OP1240/OP1314), source of the gas (MPP/MCA/MC) and charcoal source (beta-cyclodextrin) three components are added in high mixer with the rotating speed mixing 1-5min of 500r/min;
(4) the blended material of step (2) is added Banbury mixer, controlled working temperature is 185 ~ 205 DEG C, rotating speed 90 ~ 120 revs/min, after internally mix 3min, adds step (3) gained Intumescent Retardant System, continues the blended 5min of internally mix;
(5) step (4) gained material is added Single screw extrusion dicing machine immediately, controlled working temperature is 135 ~ 160 DEG C, extruding pelletization, obtains described halogen-free expanded flame-retardant thermoplastic polyether ester elastomer.
Embodiment 1
The composition of raw materials of halogen-free expanded flame-retardant TPEE prepared by the present embodiment is as follows:
Embodiment 2
The composition of raw materials of halogen-free expanded flame-retardant TPEE prepared by the present embodiment is as follows:
Embodiment 3
The composition of raw materials of halogen-free expanded flame-retardant TPEE prepared by the present embodiment is as follows:
Embodiment 4
The composition of raw materials of halogen-free expanded flame-retardant TPEE prepared by the present embodiment is as follows:
Embodiment 5
The composition of raw materials of halogen-free expanded flame-retardant TPEE prepared by the present embodiment is as follows:
Embodiment 6
The composition of raw materials of halogen-free expanded flame-retardant TPEE prepared by the present embodiment is as follows:
The halogen-free expanded flame-retardant TPEE obtained to the composition of raw materials processing in above-described embodiment 1 ~ 6 carries out flame retardant properties test, and according to UL94 standard, UL94 test all can reach 1.6mmV-0 rank.
Above to invention has been detailed description; its object is to allow the understanding being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed within protection scope of the present invention.
Claims (8)
1. beta-cyclodextrin is the expandable flame retardant thermoplastic polyether ester elastomer in charcoal source, it is characterized in that, according to the mass fraction, its material component comprises:
Wherein, described thermoplastic polyether ester elastomer is the line-type block polymer that a class contains the hard section of polybutylene terephthalate and soft section of aliphatic polyether;
Described phosphorus nitrogen Intumescent Retardant System is mixed by acid source, source of the gas and charcoal source component; Described acid source and source of the gas are respectively a kind of in organic phosphonateflame retardant and trimeric cyanamide based flame retardant or both combinations, and described charcoal source is beta-cyclodextrin.
2. polyester elastomer according to claim 1, is characterized in that, the relative molecular mass of described polyester elastomer is 30,000 ~ 60,000g/mol, and fusing point is 170 ~ 195 DEG C, and shore hardness is 30 ~ 45D.
3. polyester elastomer according to claim 1, is characterized in that, described organic hypophosphite fire retardant is the Exolit series organic secondary phosphine acid salt that Clariant is produced, and is selected from the one in OP935, OP1240, OP1314.
4. polyester elastomer according to claim 1, is characterized in that, described trimeric cyanamide based flame retardant is one or more in trimeric cyanamide, melamine polyphosphate, melamine cyanurate.
5. polyester elastomer according to claim 1, is characterized in that, as the described beta-cyclodextrin in charcoal source without secondary treatment.
6. polyester elastomer according to claim 1, is characterized in that, described fire retarding synergist is anti-dripping agent, is selected from one or both in organic nano imvite, polydimethylsiloxane.
7. polyester elastomer according to claim 1, is characterized in that, described oxidation inhibitor is one or both in irgasfos 168 and antioxidant 1010.
8. the arbitrary described method for preparing polyether ester elastomer of claim 1 to 7, is characterized in that, comprise the steps:
(1) take raw material according to mass fraction according to claim 1, dry stand-by;
(2) thermoplastic polyether ester elastomer, fire retarding synergist and oxidation inhibitor that step (1) obtains are added high-speed mixer and mixing even;
(3) acid source step (1) obtained, source of the gas and three, charcoal source component add in high mixer, mix, are re-dubbed Intumescent Retardant System;
(4) mixture of step (2) gained is added in Banbury mixer, controlled working temperature is 185 ~ 205 DEG C, rotating speed is 90 ~ 120 revs/min, adds the Intumescent Retardant System of step (3) gained, continue banburying blended after material melts is complete;
(5) product of step (4) is added Single screw extrusion dicing machine fast, controlled working temperature is 135 ~ 160 DEG C, extruding pelletization, obtains the expandable flame retardant thermoplastic polyether ester elastomer that described beta-cyclodextrin is charcoal source.
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Cited By (6)
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CN105859915A (en) * | 2016-06-12 | 2016-08-17 | 沈阳化工大学 | Preparation method of environment-friendly biobase three-source-integrated fire retardant |
WO2017172723A1 (en) * | 2016-03-31 | 2017-10-05 | E I Du Pont De Nemours And Company | Halogen free flame retardant thermoplastic elastomer compositions containing cyclodextrins |
CN109266007A (en) * | 2018-09-27 | 2019-01-25 | 唐山师范学院 | Expandable flame retardant room temperature vulcanized silicone rubber formula and expandable flame retardant room temperature vulcanized silicone rubber |
CN109608870A (en) * | 2018-12-03 | 2019-04-12 | 特塑(大连)高分子材料有限公司 | A kind of low precipitation halogen-free reinforced nylon modified material |
CN111691197A (en) * | 2020-06-24 | 2020-09-22 | 刘家浩 | Washable flame-retardant non-woven fabric and preparation method thereof |
CN113214656A (en) * | 2021-06-02 | 2021-08-06 | 镇江景宇管道设备有限公司 | Intumescent flame retardant taking octacyclodextrin POSS as carbon source and application thereof |
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CN103403077A (en) * | 2011-03-02 | 2013-11-20 | 纳幕尔杜邦公司 | Low smoke halogen free flame retardant thermoplastic elastomer compositions containing zeolites |
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CN103403077A (en) * | 2011-03-02 | 2013-11-20 | 纳幕尔杜邦公司 | Low smoke halogen free flame retardant thermoplastic elastomer compositions containing zeolites |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2017172723A1 (en) * | 2016-03-31 | 2017-10-05 | E I Du Pont De Nemours And Company | Halogen free flame retardant thermoplastic elastomer compositions containing cyclodextrins |
CN109071872A (en) * | 2016-03-31 | 2018-12-21 | 纳幕尔杜邦公司 | Halogen-free flame-retardant thermoplastic elastomer composition comprising cyclodextrin |
US20190106568A1 (en) * | 2016-03-31 | 2019-04-11 | E. I. Du Pont De Nemours And Company | Halogen free flame retardant thermoplastic elastomer compositions containing cyclodextrins |
CN105859915A (en) * | 2016-06-12 | 2016-08-17 | 沈阳化工大学 | Preparation method of environment-friendly biobase three-source-integrated fire retardant |
CN105859915B (en) * | 2016-06-12 | 2018-04-27 | 沈阳化工大学 | A kind of preparation method of environment-friendly and bio base " three-source integrated " fire retardant |
CN109266007A (en) * | 2018-09-27 | 2019-01-25 | 唐山师范学院 | Expandable flame retardant room temperature vulcanized silicone rubber formula and expandable flame retardant room temperature vulcanized silicone rubber |
CN109608870A (en) * | 2018-12-03 | 2019-04-12 | 特塑(大连)高分子材料有限公司 | A kind of low precipitation halogen-free reinforced nylon modified material |
CN111691197A (en) * | 2020-06-24 | 2020-09-22 | 刘家浩 | Washable flame-retardant non-woven fabric and preparation method thereof |
CN111691197B (en) * | 2020-06-24 | 2021-06-25 | 常州市佳胜无纺布有限公司 | Washable flame-retardant non-woven fabric and preparation method thereof |
CN113214656A (en) * | 2021-06-02 | 2021-08-06 | 镇江景宇管道设备有限公司 | Intumescent flame retardant taking octacyclodextrin POSS as carbon source and application thereof |
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