CN105385122B - Application of bridged DOPO-based compound, product thereof and preparation method of product - Google Patents
Application of bridged DOPO-based compound, product thereof and preparation method of product Download PDFInfo
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- CN105385122B CN105385122B CN201510669828.0A CN201510669828A CN105385122B CN 105385122 B CN105385122 B CN 105385122B CN 201510669828 A CN201510669828 A CN 201510669828A CN 105385122 B CN105385122 B CN 105385122B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000004626 polylactic acid Substances 0.000 claims abstract description 41
- 239000003063 flame retardant Substances 0.000 abstract description 34
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 27
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000007792 addition Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004637 bakelite Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- -1 boron phenol Urea formaldehyde Chemical compound 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VYGRRCKMMADGBB-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] phosphono hydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O VYGRRCKMMADGBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses an application of a bridged DOPO-based compound, a product thereof and a preparation method of the product. The bridged DOPO-based compound is used as a flame retardant and a transparent nucleating agent of a polylactic acid material; the addition amount of the compound is small, but the flame retardant effect of the product of the compound is good, and mechanical properties and optical properties of the material can be effectively ensured; and the bridged DOPO-based compound can be used as an injection-level electric product, a sheet-level decorative plate and the like. The application of the bridged DOPO-based compound, the product thereof and the preparation method of the product have the advantages of simplicity and easiness in use, extensive material sources, low cost and good application effect.
Description
Technical field
The present invention relates to technical field of polymer materials, especially a kind of application of bridge chain DOPO based compounds and products thereof
And products thereof preparation method.
Background technology
Oil based polyalcohol is the main source of conventional polymeric materials, but its preparation process needs to consume substantial amounts of oil
And natural gas resource.Oil and natural gas resource increasingly depleted, will use formation challenge to oil based polyalcohol；Meanwhile, stone
Oil based polymers can cause in use serious white pollution, using burn and garbage loading embeading by the way of all can produce or
Person causes serious environmental problem indirectly.Therefore, the environment-friendly material that can be recycled will become one of polymer preparation
Important development direction.Used as a kind of non-petroleum base biodegradable polymer, polylactic acid is always in material science
The focus of research.But, poly-lactic acid material easy firing similar with other macromolecular materials, and molten drop phenomenon is serious when burning, sternly
Constraining it again has the application in flame-retardancy requirements field in electronic product, automotive upholstery, household electrical appliances etc., therefore, in order to expand poly- breast
The application of acid, and meet flame-retardancy requirements of the people to material, the flame-retardant modified research to polylactic acid has caused people
Attention.
At present to the flame-retardant modified mainly by adding addition type or reactive flame retardant to obtain of macromolecular material, and
To polylactic acid it is fire-retardant be concentrated mainly on by additive flame retardant it is flame-retardant modified to carry out.Flame-proof modifier used includes bromine
System, chlorine system, phosphorus system, nitrogen system, silicon systems and inorganic combustion inhibitor etc..Because the use of halogen flame can be caused in combustion
The toxic gas such as secondary pollution and generation bioxin, are abandoned.The halogen-free flame retardants for being applied to polylactic acid is mainly intumescent
Fire retardant and inorganic combustion inhibitor.Restricted problem when expansion type flame retardant and inorganic combustion inhibitor application is that its addition is larger,
Polylactic acid physical and mechanical propertiess, therefore its flame retarding efficiency can be affected still to have much room for improvement.Another kind of halogen-free flame-retardant system is organophosphors
Flame-retardant system, addition organophosphors flame-retardant system in poly-lactic acid material bad dispersibility and need a large amount of additions.Therefore, develop organic
The key of phosphorus fire retardant is the addition that reduce fire retardant to greatest extent.
A kind of flame-retardant polylactic acid material is disclosed in patent CN102382433A.The flame-proof polylactic acid material of every 100 weight portion
Contain 80～95 parts of polylactic resin, 1～15 part of compound between graphite layers, 2～10 parts of fire retardant, antioxidant 0.01～1 in material
0.5～1 part of part, 1～14 part of carbon forming agent and synergist；Wherein the total mass fraction of compound between graphite layers and carbon forming agent be 2～
16 parts.Compound between graphite layers are the graphite containing catalyst component or rare earth, and synergist is clay or solid superacid.Fire retardant is
One or more in polyphosphoric acid amine, melamine Quadrafos, pentaerythritol diphosphate.The clay be sodium-based montmorillonite,
At least one in alkylammonium salt intercalated montmorillonite, quaternary alkylphosphonium salt intercalated montmorillonites.Patent CN102134379 A discloses one kind
Halogen-free flame-proof polylactic acid material and its manufacture method.Including following component：By weight percentage, 50%-80% polylactic acid base material,
5%-40% halogen-free flame retardants, 0.1%-1.5% dispersing aiies, 10%-30% degradable toughened resins.Patent CN104031364A is disclosed
A kind of enhancing flame-retardant polylactic acid material and preparation method thereof.The poly-lactic acid material includes polylactic acid particle, modified ambary, boron phenol
Urea formaldehyde and macromolecule polycondenseng phosphate.The enhancing flame-retardant polylactic acid material preparation method is：（1）First ambary is carried out at alkali
After reason, then with the modified ambary of vinyltrimethoxy silane, crush standby；（2）By a certain proportion of polylactic acid particle with it is modified
Ambary, boron bakelite resin, macromolecule polycondenseng phosphate are added in torque rheometer, are obtained by ambary, boron bakelite resin, height
Molecule polycondenseng phosphate strengthens fire-retardant poly-lactic acid material.But due to auxiliary agent such as compound between graphite layers, clay or dispersion
The introducing of agent etc. results in polylactic acid color and transparent performance occurs greatly change, limits its answering as transparent material
With.
Patent CN104086593 discloses a kind of compound that can be used as novel halogen-free flame-retardant, by aryl ketones and DOPO
It is obtained under acidic catalyst effect.But, simply indicate in the patent using such compound as fire retardant application.This
Invention mainly points out that such compound, as the extensive application of nucleator, when adding in poly-lactic acid material, can make polylactic acid
The transparency is presented, while having fire resistance concurrently.
The content of the invention
The purpose of the present invention is：A kind of preparation side of application of bridge chain DOPO based compounds and products thereof and products thereof is provided
Method, it can be used in poly-lactic acid material as transparent nucleater, it is possible to reduce the fire retardant addition of flame-retardant system, protected
Ensure the mechanical property and optical property of material while card flame retardant effect, to overcome the deficiencies in the prior art.
What the present invention was realized in：Bridge chain DOPO based compounds answering as transparent nucleater in poly-lactic acid material
With.
Transparent halogen-free flameproof poly-lactic acid material, calculates according to the mass fraction, including 90-98 parts polylactic acid and 2-10 part bridge chains
DOPO based compounds.
The grain diameter of described bridge chain DOPO based compounds is 0.2 μm -5 μm.
The preparation method of transparent halogen-free flameproof poly-lactic acid material, by above-mentioned parts by weight each component is taken,
1）Polylactic acid and bridge chain DOPO based compounds are dried into 2-3 hours at 85-90 DEG C；
2）Again the mix homogeneously in blender by dried bridge chain DOPO based compounds and polylactic acid, obtains mixed base
Material；
3）Finally by step 2）The mixed resin melting extrusion pelletize of middle acquisition obtains halogen-free flame-proof polylactic acid material.
Bridge chain DOPO based compounds of the present invention are the compound disclosed in patent CN104086593.
As a result of above-mentioned technical proposal, compared with prior art, the present invention is using bridge chain DOPO based compounds as poly-
The fire retardant and transparent nucleater of lactate material, its addition is little, but the good flame retardation effect of its product, and material can be effectively ensured
Mechanical property and optical property, can be used as injection grade electronic product, sheet material level dalle etc..Simple, material of the invention
Material wide material sources, with low cost, using effect is good.
Description of the drawings,
Accompanying drawing 1 is sample contrast after comparative example 1 and the vertical combustion of embodiment 1；
Accompanying drawing 2 is sample contrast after comparative example 1, comparative example 2 and the vertical combustion of embodiment 2.
Specific embodiment,
Embodiments of the invention 1：Bridge chain DOPO based compounds are in poly-lactic acid material as the application of transparent nucleater.
Transparent halogen-free flameproof poly-lactic acid material, calculates according to the mass fraction, including 95 parts of polylactic acid and 5 parts of bridge chain DOPO bases
Compound；The grain diameter of described bridge chain DOPO based compounds is 0.2 μm -5 μm.
The preparation method of transparent halogen-free flameproof poly-lactic acid material, by above-mentioned parts by weight each component is taken,
1）Polylactic acid and bridge chain DOPO based compounds are dried into 2-3 hours at 85-90 DEG C；
2）Again the mix homogeneously in blender by dried bridge chain DOPO based compounds and polylactic acid, obtains mixed base
Material；
3）Finally by step 2）The mixed resin melting extrusion pelletize of middle acquisition obtains halogen-free flame-proof polylactic acid material.
Embodiments of the invention 2：Transparent halogen-free flameproof poly-lactic acid material, calculates according to the mass fraction, including 90 parts of polylactic acid
And 10 parts of bridge chain DOPO based compounds；The grain diameter of described bridge chain DOPO based compounds is 0.2 μm -5 μm.
Preparation method is with embodiment 1.
The structural formula of the bridge chain DOPO based compounds that above-described embodiment is adopted for：
Comparative example 1：By pure polylactic acid base material by same processing mode as a comparison case 1.
Comparative example 2：By the phosphorus flame retardant OP1230 of the presently commercially available German Clariant companies being most widely used（Add
Dosage is 10 parts）By same processing mode, as a comparison case 2.
Table 1 is comparative example 1, comparative example 2 and embodiment 1 and the concrete contrast test data of embodiment 2.Fig. 1 is comparative example 1
（PLA）, comparative example 2（FRPLA2）With embodiment 2（FRPLA1）Batten photo after vertical burn test.
The fire proofing Mechanics Performance Testing prepared under the Different adding amount of table 1 and UL-94 test datas,
As seen from Table 1, when fire retardant addition is 5wt%, its tensile strength improves 3.9%, and fire-retardant rank reaches
UL-94 V-1 levels, when fire retardant addition is 10wt%, although its tensile strength is slightly reduced, fire-retardant rank reaches
UL-94 V-0 levels, while sample remains in that the good transparency, and comparative example 2 reduces the tensile strength of fire proofing
6.1%.Comparative example 1, comparative example 2 is as shown in Figure 1 with the contrast after the vertical combustion of embodiment 2.As can be seen that embodiment 2 is presented
The excellent transparency, and comparative example 2 is entirely then milky.
Above content is to combine specific preferred implementation further description made for the present invention, it is impossible to assert
The present invention be embodied as be confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of without departing from present inventive concept, some equivalent substitutes or obvious modification are made, and performance or purposes are identical, all should
It is considered as belonging to protection scope of the present invention.
Claims (1)
1. a kind of bridge chain DOPO based compounds in poly-lactic acid material as the application of transparent nucleater, it is characterised in that：The bridge
The structural formula of chain DOPO based compounds is,
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| CN201510669828.0A CN105385122B (en) | 2015-10-18 | 2015-10-18 | Application of bridged DOPO-based compound, product thereof and preparation method of product |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106280341B (en) * | 2016-08-31 | 2018-12-14 | 江林（贵州）高科发展股份有限公司 | Halogen-free flameproof long glass fiber reinforced lactic acid composite material and preparation method thereof |
| JP7114895B2 (en) * | 2017-12-19 | 2022-08-09 | 三菱ケミカル株式会社 | polyethylene terephthalate film |
| CN108059824B (en) * | 2017-12-20 | 2020-09-04 | 贵州省材料产业技术研究院 | Transparent flame-retardant high-temperature nylon and preparation method thereof |
| CN108485208A (en) * | 2018-03-29 | 2018-09-04 | 贵州省材料产业技术研究院 | A kind of DOPO derivatives Flame-retardant PET transparent composite and preparation method |
| CN108822508A (en) * | 2018-05-17 | 2018-11-16 | 贵州省材料产业技术研究院 | A kind of flame-proof polylactic acid composite material and preparation method and application |
| CN111763412A (en) * | 2020-05-29 | 2020-10-13 | 贵州省材料产业技术研究院 | Flame-retardant toughened polylactic acid-based composite material and preparation and application thereof |
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| CN102174250A (en) * | 2011-03-15 | 2011-09-07 | 上海大学 | Organic nucleating agent for rapidly crystallizing polylactic acid and rapidly-crystallized polylactic acid resin of organic nucleating agent |
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| CN104262398A (en) * | 2014-09-23 | 2015-01-07 | 厦门大学 | Phosphorus-nitrogen type flame retardant containing active double bond as well as preparation method and application thereof |
| CN104877172A (en) * | 2015-05-13 | 2015-09-02 | 常州龙骏天纯环保科技有限公司 | Method for modifying fast-crystallization high-crystallinity polylactic acid |
| CN105001122A (en) * | 2015-07-02 | 2015-10-28 | 浙江工业大学 | Polylactic acid organic nucleating agent as well as preparation method therefor and application thereof |
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| JP3308335B2 (en) * | 1993-04-13 | 2002-07-29 | 三井化学株式会社 | Lactic acid-based polymer composition, pellets thereof, molded body thereof and molding method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174250A (en) * | 2011-03-15 | 2011-09-07 | 上海大学 | Organic nucleating agent for rapidly crystallizing polylactic acid and rapidly-crystallized polylactic acid resin of organic nucleating agent |
| CN104262398A (en) * | 2014-09-23 | 2015-01-07 | 厦门大学 | Phosphorus-nitrogen type flame retardant containing active double bond as well as preparation method and application thereof |
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| CN105001122A (en) * | 2015-07-02 | 2015-10-28 | 浙江工业大学 | Polylactic acid organic nucleating agent as well as preparation method therefor and application thereof |
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