CN112321996A - Phosphorus-containing flame-retardant degradable polyester material and preparation method thereof - Google Patents
Phosphorus-containing flame-retardant degradable polyester material and preparation method thereof Download PDFInfo
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- CN112321996A CN112321996A CN202011192876.2A CN202011192876A CN112321996A CN 112321996 A CN112321996 A CN 112321996A CN 202011192876 A CN202011192876 A CN 202011192876A CN 112321996 A CN112321996 A CN 112321996A
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- phosphorus
- containing flame
- flame retardant
- degradable polyester
- polyester material
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- 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 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 64
- 229920000728 polyester Polymers 0.000 title claims abstract description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 39
- 239000011574 phosphorus Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 2-carboxyethyl phenyl hypophosphorous acid Chemical compound 0.000 claims abstract description 25
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 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 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 239000003607 modifier Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000002667 nucleating agent Substances 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 239000004970 Chain extender Substances 0.000 claims description 13
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 239000004626 polylactic acid Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000011858 nanopowder Substances 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 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 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 description 18
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000243 solution Substances 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
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of degradable materials, in particular to a phosphorus-containing flame-retardant degradable polyester material and a preparation method thereof, wherein the phosphorus-containing flame-retardant degradable polyester material comprises degradable polyester and a phosphorus-containing flame retardant; the phosphorus-containing flame retardant comprises one or more of a phosphine-containing flame retardant, 2-carboxyethyl phenyl hypophosphorous acid, DOPO and a modifier thereof; the method comprises weighing the materials of each component, and mixing the materials; placing the mixed materials in a reactor, melting and extruding at the temperature of 150-250 ℃, cooling and granulating to prepare the phosphorus-containing flame-retardant degradable polyester material; the invention provides a degradable material with good flame retardant property and mechanical property and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of degradable materials, in particular to a phosphorus-containing flame-retardant degradable polyester material and a preparation method thereof.
Background
Most of foamed plastic products on the market at present are petroleum-based products, such as polyvinyl chloride, polystyrene, polypropylene and the like, and although the products have the advantages of low density, high strength, low price and the like, the products are difficult to degrade or cannot be degraded, and the generated white pollution becomes a worldwide public hazard which harms social environment, and the sustainable development of social economy and environment is seriously hindered.
With the development of times, the development of degradable flame-retardant foam plastic to replace non-degradable plastic is imperative. The biodegradable polymer mainly comprises polylactic acid (PLA), Polybutylene Butyrate (PBS), Polycaprolactone (PCL), Polyhydroxyalkanoate (PHA), polybutylene adipate/terephthalate (PBAT) and the like, and the materials have important significance for human sustainable development.
From patents published at home and abroad, the degradable material is mainly applied to the field of medicine, as long as the degradable material relates to a drug microsphere carrier, an anti-adhesion film, a biological catheter, an orthopedic fixture, an orthopedic surgical device, a drug composite polymer bracket, an artificial bone and the like, and the biodegradable material is also applied to the fields of packaging, fiber, agriculture, injection molding and the like.
As a biodegradable material, there is currently no commercial supply of flame retardant materials. At present, the commonly used flame retardant modification of the polymer mainly adopts a method of adding organic or inorganic filling type or micromolecular flame retardant. The halogen-containing flame retardant has less addition amount and high flame-retardant efficiency, but the halogen-containing flame retardant can generate toxic gas in the combustion process to cause secondary pollution to the environment. Therefore, halogen-free flame retardant modification is the mainstream of market development. There are few reports on halogen-free flame retardation while satisfying the requirements of degradable polyester materials. Chinese patent CN201610272620.X discloses a PLA toughening modified composite material, which adopts a hypophosphite/phosphonate flame retardant with small molecular weight, poor compatibility with a base material and easy precipitation.
Therefore, a halogen-free flame-retardant degradable polyester material is urgently needed to be found, so that the flame retardant property of the material is improved, the melt strength of the material is increased, and the material can be biologically decomposed.
Disclosure of Invention
Aiming at the problems, the invention discloses a degradable material with good flame retardant property and mechanical property and a preparation method thereof.
In a first aspect of the invention, a phosphorus-containing flame retardant degradable polyester material is provided, which comprises degradable polyester and a phosphorus-containing flame retardant;
the phosphorus-containing flame retardant comprises one or more of a phosphine-containing flame retardant, 2-carboxyethyl phenyl hypophosphorous acid, DOPO and a modifier thereof.
In the invention, the phosphine-containing flame retardant and the degradable polyester can generate ester exchange reaction, the 2-carboxyethyl phenyl hypophosphorous acid and the degradable polyester can generate ester exchange reaction, and the DOPO and the degradable polyester can generate ring-opening chain extension reaction.
Preferably, the degradable polyester comprises one or more of polylactic acid, polybutylene butyrate, polycaprolactone, polyhydroxyalkanoate and polybutylene adipate/terephthalate.
Preferably, the phosphine-containing flame-retardant oligomer or macromolecule comprises polyphosphonate shown as the following formula I and derivatives thereof, or polyphosphonate or phosphonate-carbonate copolymer shown as the following formula II;
wherein R1, R2 include:
r3 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl or sec-butyl;
r4 is selected from
R5 is selected from
Wherein R1, R2 and R3 are the same as R1, R2 and R3 in the formula I.
Preferably, the composite material also comprises an accelerator, a nucleating agent, an antioxidant and a chain extender.
Preferably, the phosphorus-containing flame-retardant degradable polyester material comprises the following components in parts by weight:
preferably, the promoter comprises all or part of a metal saponifier, such as TR030H from shanghai landscaping chemical.
Preferably, the antioxidant comprises one or more of hindered phenols, phosphonites, aromatic amines and thiosulfate.
Preferably, the chain extender comprises one or more of an acid anhydride, an oxazoline compound and an isocyanate; further preferably, the anhydride comprises PMDA, the oxazoline compound comprises BOZ, and the isocyanate comprises MDI, HDI, TDI, and the like.
Preferably, the nucleating agent comprises an easily dispersible nano powder material; further preferably, the nano powder material easy to disperse is selected from but not limited to at least one of BF nucleating agent series, carbon nano tube, nano titanium dioxide, talcum powder, modified calcium carbonate, graphene, carbon black, wollastonite powder, montmorillonite, kaolin or tetrafluoroethylene powder; even more preferred, from the series of BF nucleating agents. The BF nucleating agent series is a BF nucleating agent series of Shanghai Zhuang Jing chemical engineering, and comprises but is not limited to BF-20, BF-NC and BF-sil.
In a second aspect of the present invention, there is provided a method for preparing a phosphorus-containing flame retardant degradable polyester material, comprising the steps of:
s1, weighing the materials of each component, and mixing the materials;
s2, placing the mixed materials in a double-screw extruder, melting and extruding at the temperature of 150-250 ℃, cooling and granulating to prepare the phosphorus-containing flame-retardant degradable polyester material.
Preferably, the process of mixing materials can be completed by a pipeline reactor or a tank reactor. Wherein the pipe reactor needs to comprise a screw assembly for pushing high viscosity melt, or a pump structural unit.
Preferably, the synthesis process also comprises the step of performing liquid-phase tackifying, solid-phase tackifying or screw extrusion tackifying on the phosphorus-containing flame-retardant degradable polyester material. The molecular weight of the degradable polyester can be improved through tackifying; the molecular weight of the flame retardant is improved; the degradation efficiency is increased.
The phosphorus-containing flame-retardant degradable polyester material provided by the invention has good processing performance, is particularly suitable for processing modes with certain stretching requirements, such as film blowing, tape casting, double drawing, spinning and the like, and the obtained material, film sheet and fiber have good flame-retardant and biodegradable properties; the flame retardant grade of the phosphorus-containing flame retardant degradable polyester provided by the invention is VTM0(GB 4943.1-2011), building B1(GB8624-1997), V0(UL94) and M1(NFP 92-507).
Compared with the prior art, the invention has the following advantages or beneficial effects:
1. the polyester material adopted by the invention is degradable and is a green and environment-friendly material;
2. the phosphorus-containing flame-retardant degradable polyester material prepared by the invention can also show excellent flame retardant property and mechanical property under the condition of adding less flame retardant;
3. the flame retardant used in the invention exists in the polyester in the form of macromolecular chains, the melt strength of the polyester is improved to a certain extent, the flame retardant is not separated out, and the flame retardant effect can be maintained for a long time;
4. the flame retardant is introduced into a polyester main chain by an ester exchange method or ring opening chain extension, and the bonding force of the flame retardant and the polyester is a chemical bond;
5. the phosphorus-containing flame-retardant degradable polyester material prepared by the invention can be used for film sheets, fibers and the like, and has a wide application range.
Detailed Description
Those skilled in the art will appreciate that variations may be implemented by those skilled in the art in combination with the prior art and the above-described embodiments, and will not be described herein in detail. Such variations do not affect the essence of the present invention and are not described herein.
Example 1
20 wt% of polyphosphonate a (formula:
Example 2
Uniformly mixing 18.0 wt% of polyphosphonate A, 0.4 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant), 79.6 wt% of PBAT resin and 2.0 wt% of other additives (1.0 wt% of chain extender BOZ and 1.0 wt% of nucleating agent BF-NC) in a high-speed mixer, adding the mixture into a double-screw extruder, carrying out melt extrusion at 180-220 ℃, cooling and granulating. And (5) performing sample making by an injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 3
18.0% by weight of phosphonate-carbonate copolymer B(the structural formula is:
r1 is methyl
R2 is
R3 is methyl, n is 6), 0.4 wt% of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester (antioxidant), 78.6 wt% PBAT resin and 3.0 wt% of other additives (2.0 wt% of nucleating agent BF-sil and 1.0 wt% of chain extender HDI) are uniformly mixed in a high-speed mixer, added into a double-screw extruder, melted and extruded at 180-220 ℃, and cooled and granulated. And (4) proofing by an injection molding machine, and proofing by the injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 4
The preparation method comprises the steps of uniformly mixing 18.0 wt% of CEPPA, 0.5 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant), 78.5 wt% of PBAT resin and 3.0 wt% of other additives (2.0 wt% of nucleating agent BF-20 and 1.0 wt% of chain extender MDI) in a high-speed mixer, adding the mixture into a double-screw extruder, carrying out melt extrusion at 180-220 ℃, cooling and granulating. And (4) proofing by an injection molding machine, and proofing by the injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 5
18.0 wt% of DOPO, 0.5 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant), 78.5 wt% of PBAT resin and 3.0 wt% of other auxiliary agents (2.0 wt% of nucleating agent BF-NC,1.0 wt% of chain extender HDI) are uniformly mixed in a high-speed mixer, added into a double-screw extruder, melted and extruded at 180-220 ℃, and cooled and granulated. And (4) proofing by an injection molding machine, and proofing by the injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 6
10.0 wt% of polyphosphonate A, 8.0 wt% of CEPPA, 0.5 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant), 78.5 wt% of PBAT resin and 3.0 wt% of other additives (2.0 wt% of nucleating agent BF-sil and 1.0 wt% of chain extender PMDA) are uniformly mixed in a high-speed mixer, added into a double-screw extruder, melted and extruded at 180-220 ℃, and cooled and granulated. And (4) proofing by an injection molding machine, and proofing by the injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 7
18.0 wt% of DOPO, 0.5 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant), 79.5 wt% of PLA resin and 2.0 wt% of other auxiliary agents (1.0 wt% of accelerant TR030H in Shanghai Zhuang Jing chemical engineering and 1.0 wt% of nucleating agent BF-20) are uniformly mixed in a high-speed mixer, added into a double-screw extruder, rotated at 50 revolutions per minute, melted and extruded at 180-220 ℃, and cooled and granulated. And (4) proofing by an injection molding machine, and proofing by the injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 8
Mixing 10.0 wt% of phosphonate-carbonate copolymer B, 8.0 wt% of DOPO, 0.4 wt% of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant), 79.6 wt% of PBAT resin and 2.0 wt% of other auxiliary agents (1.0 wt% of chain extender PMDA and 1.0 wt% of nucleating agent BF-sil) in a high-speed mixer uniformly, adding the mixture into a double-screw extruder, carrying out melt extrusion at 180-220 ℃, cooling and granulating. And (4) proofing by an injection molding machine, and proofing by the injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 9
Uniformly mixing 18.0 wt% of polyphosphonate A, 0.4 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant), 48.6 wt% of PBAT resin, 30.0 wt% of PCL resin and 3.0 wt% of other auxiliary agents (1.0 wt% of chain extender PMDA, 1.0 wt% of nucleating agent BF-NC and 1.0 wt% of promoter TR030H of Shanghai Zhuang Jing chemical) in a high-speed mixer, adding into a double-screw extruder, performing melt extrusion at 180-220 ℃, and cooling and granulating. And (4) proofing by an injection molding machine, and proofing by the injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
Example 10
8.0 wt% of polyphosphonate A, 0.4 wt% of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant), 87.6 wt% of PBAT resin and 4.0 wt% of other additives (1.0 wt% of chain extender PMDA, 1.0 wt% of nucleating agent BF-sil and 2.0 wt% of promoter TR030H in Shanghai Zhuang Jing chemical) are uniformly mixed in a high-speed mixer, added into a double-screw extruder, melted and extruded at 180-220 ℃, and cooled and granulated. And (5) performing sample making by an injection molding machine to obtain a standard sample strip for testing mechanical properties, flame retardant properties and the like.
The mechanical property and the flame retardant property test results of the phosphorus-containing flame retardant degradable polyester materials of examples 1-10 are shown in the following table 1.
TABLE 1
As can be seen from the results in Table 1, the phosphorus-containing flame retardant degradable polyester materials provided in examples 1 to 10 have tensile strength of 32 to 44MPa and melt index of 3.4 to 4.7g/10 min. As can be seen, the phosphorus-containing flame-retardant degradable polyester materials provided in examples 1 to 10 have better mechanical properties. In addition, the flame retardant grades of the phosphorus-containing flame retardant degradable polyester materials of examples 1 to 10 are all V0, and it can be seen that the phosphorus-containing flame retardant degradable polyester materials provided by examples 1 to 10 have better flame retardant property.
The above description is of the preferred embodiment of the invention. It is to be understood that the invention is not limited to the particular embodiments described above, in that devices and structures not described in detail are understood to be implemented in a manner common in the art; those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or modify equivalent embodiments to equivalent variations, without departing from the spirit of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (10)
1. The phosphorus-containing flame-retardant degradable polyester material is characterized by comprising degradable polyester and a phosphorus-containing flame retardant;
the phosphorus-containing flame retardant comprises one or more of a phosphine-containing flame retardant, 2-carboxyethyl phenyl hypophosphorous acid, DOPO and a modifier thereof.
2. The phosphorus-containing flame retardant degradable polyester material of claim 1, wherein the degradable polyester comprises one or more of polylactic acid, polybutylene butyrate, polycaprolactone, polyhydroxyalkanoate, and polybutylene adipate/terephthalate.
3. The phosphorus-containing flame retardant degradable polyester material of claim 1 or 2, wherein the phosphorus-containing flame retardant oligomer or macromolecule comprises polyphosphonate represented by formula I and derivatives thereof, or polyphosphonate or phosphonate-carbonate copolymer represented by formula II;
wherein R1, R2 include:
r3 includes methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, or sec-butyl;
r4 includes
R5 includes
Wherein R1, R2 and R3 are the same as R1, R2 and R3 in the formula I.
4. The phosphorus-containing flame retardant degradable polyester material of claim 1, further comprising one or more of an accelerator, a nucleating agent, an antioxidant, and a chain extender.
5. The phosphorus-containing flame retardant degradable polyester material of claim 4, wherein the phosphorus-containing flame retardant degradable polyester material comprises the following components in parts by weight:
6. the phosphorus-containing flame retardant degradable polyester material of claim 4 or 5, wherein the accelerator comprises a metal saponifier and the antioxidant comprises one or more of hindered phenols, phosphonites, aromatic amines, thiosulfate.
7. The phosphorus-containing flame retardant degradable polyester material of claim 4 or 5, wherein the chain extender comprises one or more of acid anhydride, oxazoline compound and isocyanate.
8. The phosphorus-containing flame retardant degradable polyester material of claim 4 or 5, wherein the nucleating agent comprises an easily dispersible nanopowder material.
9. The phosphorus-containing flame retardant degradable polyester material of claim 8, wherein the easily dispersible nano powder material comprises one or more of BF nucleating agent series, carbon nano tubes, nano titanium dioxide, talcum powder, modified calcium carbonate, graphene, carbon black, wollastonite powder, montmorillonite, kaolin or tetrafluoroethylene powder.
10. A method for preparing the phosphorus-containing flame-retardant degradable polyester material as claimed in any one of claims 1 to 9, which comprises the following steps:
s1, weighing the materials of each component, and mixing the materials;
s2, placing the mixed materials in a kettle type reactor or a pipeline type reactor, melting and extruding at the temperature of 150 ℃ and 250 ℃, cooling and granulating to prepare the phosphorus-containing flame-retardant degradable polyester material.
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