CN105646938A - Additive composition for polymers, preparation method thereof and flame-retardant thermoplastic polymer molding material composed of same - Google Patents
Additive composition for polymers, preparation method thereof and flame-retardant thermoplastic polymer molding material composed of same Download PDFInfo
- Publication number
- CN105646938A CN105646938A CN201610057649.6A CN201610057649A CN105646938A CN 105646938 A CN105646938 A CN 105646938A CN 201610057649 A CN201610057649 A CN 201610057649A CN 105646938 A CN105646938 A CN 105646938A
- Authority
- CN
- China
- Prior art keywords
- component
- polymer
- compositions
- additives
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000000654 additive Substances 0.000 title claims abstract description 61
- 229920000642 polymer Polymers 0.000 title claims abstract description 55
- 230000000996 additive effect Effects 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 12
- 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 abstract description 16
- 239000012778 molding material Substances 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 150000003839 salts Chemical class 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 17
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- 239000004677 Nylon Substances 0.000 claims description 12
- 229920001778 nylon Polymers 0.000 claims description 12
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical group [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 8
- 229920001955 polyphenylene ether Polymers 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000005819 Potassium phosphonate Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 4
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 238000001125 extrusion Methods 0.000 abstract description 3
- 238000003754 machining Methods 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- -1 hypophosphorous acid ion Chemical class 0.000 description 37
- LQQZCRDKYVCYAW-UHFFFAOYSA-N diethylphosphinic acid;sodium Chemical compound [Na].CCP(O)(=O)CC LQQZCRDKYVCYAW-UHFFFAOYSA-N 0.000 description 18
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 17
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 14
- 238000009413 insulation Methods 0.000 description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 14
- 238000010792 warming Methods 0.000 description 13
- 230000036571 hydration Effects 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 9
- LYYXRDZATAMURV-UHFFFAOYSA-N ethylphosphonous acid Chemical compound CCP(O)O LYYXRDZATAMURV-UHFFFAOYSA-N 0.000 description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000004679 31P NMR spectroscopy Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YUZPWHTZJLNXTL-UHFFFAOYSA-N [Na].CCP(O)O Chemical compound [Na].CCP(O)O YUZPWHTZJLNXTL-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000206 moulding compound Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing 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
- C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
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)
- Fireproofing Substances (AREA)
Abstract
The invention discloses an additive composition for polymers, a preparation method thereof and a flame-retardant thermoplastic polymer molding material composed of the additive composition for polymers. The additive composition for polymers comprises 80-99.99wt% of a component A di-alkylphosphinate of the structure shown in the formula (I), 0-20wt% of a component B alkylphosphite of the structure shown in the formula (II) and 0-0.9wt% of a component C phosphate of the structure shown in the formula (III), wherein the weight percent of the component B and the weight percent of the component C are not 0wt% at the same time, and the total sum of the weight percents of the component A, the component B and the component C is 100wt% all the time. Additives are applied to polymers, the corrosion degree of a flame-retardant polymer to a mixed combined device screw is greatly reduced, energy and manpower loss caused by frequent replacement of screws in the machining process is reduced while the equipment machining cost is reduced, and the whiteness of a polymer containing piece obtained through extrusion molding is superior to that of conventional polymer containing pieces modified through di-alkylphosphinate.
Description
The application is application number is 201410592746.6, and the applying date is 2014-10-29, and invention and created name is the divisional application of " a kind of compositions of additives for polymer and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material ".
Technical field
The present invention relates to a kind of compositions of additives for polymer, be specifically related to a kind of dialkylphosphinic salts containing phostonic acid salt and/or phosphite and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material.
Background technology
Dialkylphosphinic salts, is widely used as fire retardant, it is known that it can be synthesized by diverse ways. It is used as fire retardant at polyester, the preparation methoies that DE19910232, US6248921 two sections of patent disclosure a kind of two replace metal phosphinates as patent DE4430932 discloses two replacement metal phosphinates. The preparation method that US Patent No. 6359171B1 discloses a kind of dialkyl phosphinic acid aluminum, the method synthesizes monoalkyl phosphonate initially with yellow phosphorus, then utilize free radical cause be hydrolyzed after vinylation sour after be obtained by reacting dialkyl phosphinic acid aluminum fire retardant with aluminium salt.
Aluminum diethylphosphinate is the novel halogen-free flame-retardant agent of a kind of thermally-stabilised height, excellent fireproof performance. But find in actual applications, it is added with the flame-retardant polymer moulding compound of aluminum diethylphosphinate in the course of processing, the screw rod of compounding combination unit can be brought the corrosion of especially severe, and ambient polymer is damaged, especially can cause the degraded of polymer. It is primarily due to dialkyl phosphinic acid that dialkyl phosphinic acid aluminum is ionized under the high temperature conditions to metal ion selectively complexation, particularly the nickel of rustless steel clock, chromium etc. had higher selectivity so that in flame-retardant polymer is processed, screw rod is had heavy corrosion at dialkylphosphinic salts.We also find under study for action, and the corrosivity of screw rod is become even more serious along with the growth of its alkyl chain by dialkylphosphinic salts. In actual applications it was also found that the flame-retardant polymer being added with aluminum diethylphosphinate puts part whiteness is short of to some extent.
We are mixed into part phostonic acid salt and/or a small amount of phosphinate by the discovery studied in dialkylphosphinic salts, can alleviate the flame-retardant polymer moulding compound being added with dialkylphosphinic salts corrosion to compounding combination unit screw rod in the course of processing to a great extent, and on other performances of flame-retardant polymer almost without impact.
Patent CN103154110 discloses and is mixed into 1-80% phosphinate in dialkylphosphinic salts and plays the effect of stabilizer, we have found that, because the heat decomposition temperature of aluminium phosphite is relatively low, and in engineering plastics in the high temperature extrusion course of processing (major part engineering plastics processing temperature is above 200 DEG C) easily decomposes, its decomposition can produce meet air spontaneously inflammable severe toxicity hydrogen phosphide other, we have discovered that its content is more beneficial for corrosion resistance, stability and safety thereof lower than 1%.
We also find to be mixed into part phostonic acid salt and/or a small amount of phosphite in dialkylphosphinic salts by studying simultaneously so that be added with the flame-retardant polymer moulding compound product whiteness of dialkylphosphinic salts more preferably.
Summary of the invention
In order to solve to be added with the whiteness of the flame-retardant polymer of dialkylphosphinic salts and its moulding compound problem to the corrosion of compounding combination unit screw rod in the course of processing, it is an object of the invention to provide a kind of compositions of additives in dialkylphosphinic salts containing phostonic acid salt and/or phosphite structure and consisting of flame-proofed thermoplastic polymer in-mold moulding material. This additive application is in polymer, in the course of processing compounding combination unit Screw Corrosion degree is little, the ambient polymer extent of damage is little, and obtained flame-retardant polymer molding compositions product whiteness is better, and on other performances of flame-retardant polymer almost without impact.
The preparation method that another object of the present invention is to provide the above-mentioned compositions of additives for polymer that a kind of technological process is simple, reaction time is short, gross production rate is high.
The present invention is achieved by the following technical solutions:
A kind of compositions of additives for polymer, including:
Component A:80wt%-99.99wt% has the dialkylphosphinic salts of structure shown in formula (I),
Wherein, R1, R2 is identical or different, is expressed as ethyl, propyl group and/or butyl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
Component B:0wt%-20wt% has the phostonic acid salt of structure shown in formula II,
(II)
Wherein, R3 is expressed as ethyl, propyl group and/or butyl; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(III)
Wherein, R3 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
It is 0wt% when component B, C difference, and the summation of A, B and component C is always 100wt%.
Preferably, for the compositions of additives of polymer, it comprises:
The component A of 95wt%-99.99wt%;
The component B of 0wt%-5wt%;
The component C of 0wt%-0.9wt%;
It is 0wt% when component B, C difference, and the summation of A, B and component C is always 100wt%.
Described polymer is PBT, nylon, PPE, TPE, TPU, high-temperature nylon or epoxy resin, it is preferable that PBT, nylon or PPE.
The preparation method of the above-mentioned a kind of compositions of additives for polymer of the present invention, can one of as follows:
Method one:
A) hypophosphorous acid or its salt are added in a solvent, with olefine reaction under initiator and reaction promoter effect, the dialkyl phosphinic acid obtained or its saline solution, its solution metallizing thing reactant aqueous solution can prepare dialkylphosphinic salts;
B) adding phosphorous acid or its salt in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain phostonic acid or its saline solution, its solution metallizing thing reactant aqueous solution can prepare phostonic acid salt;
C) phosphorous acid or its salt metallizing thing are obtained by reacting phosphite;
D) product of step a and step b and/or step c gained mixed and get final product;
Wherein, described hypophosphites is sodium hypophosphite or potassium hypophosphite; Described phosphite is sodium phosphite or potassium phosphite;
Described metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe;
Or method two:
By miscible to dialkyl phosphinic acid or its saline solution and phostonic acid or its saline solution and/or phosphorous acid or its saline solution, then metallizing thing solution reaction and get final product.
Described solvent is water; Described initiator is azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator; Described alkene is one or both the mixture in ethylene and/or butylene.
Described reaction promoter is sodium borohydride or potassium borohydride.
A kind of compositions of additives for polymer of the present invention is as the purposes of fire retardant.
The invention also discloses a kind of flame-proofed thermoplastic polymer in-mold moulding material comprising above-mentioned compositions of additives, including the additive for polymer of 5-20 weight portion, the polymer of 50-70 weight portion or its mixture; Wherein, the additive for polymer includes:
Component A:80wt%-99.99wt% has the dialkylphosphinic salts of structure shown in formula (I),
Wherein, R1, R2 is identical or different, is expressed as ethyl, propyl group and/or butyl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
Component B:0wt%-20wt% has the phostonic acid salt of structure shown in formula II,
(II)
Wherein, R3 is expressed as ethyl, propyl group and/or butyl; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(III)
Wherein, R3 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
It is 0wt% when component B, C difference, and the summation of A, B and component C is always 100wt%.
Described polymer is polyester, nylon, high-temperature nylon, PPE, TPE, TPU or epoxy resin, it is preferable that polyester, nylon or PPE.
Flame-proofed thermoplastic polymer in-mold moulding material of the present invention, also includes the glass fibre of 15-30 weight portion and other auxiliary agents of 1-5 weight portion.
The present invention compared with prior art, has the advantages that
1) dialkylphosphinic salts containing phostonic acid salt and/or phosphite structure that the present invention prepares, additive as flame-retardant polymer, this additive application is in polymer, in the course of processing, greatly reduce the dialkylphosphinic salts flame-retardant polymer as additive to compounding combination unit Screw Corrosion degree, also reduce while reducing apparatus processing cost and the course of processing is frequently changed the energy and the artificial loss that screw rod causes, significantly widened this plastic additive range of application in the market;
2) dialkylphosphinic salts containing phostonic acid salt and/or phosphite structure that the present invention prepares, additive as flame-retardant polymer, this additive application is in polymer so that the polymer obtained through extrusion molding is put the polymer that part whiteness is better than conventional dialkylphosphinic salts modified and put part;
3) this additive preparation technology is simple, safety, and production cost is low, extremely has practicality.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Embodiment 1: the preparation of one-component A aluminum diethylphosphinate
By 1060.0g(10mol) a hydration sodium hypophosphite, 9.1g(0.3%mol hypophosphorous acid ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 3.0g sodium borohydride and 1500g water add in autoclave, evacuate, replace 3 times with nitrogen, evacuate, it is filled with ethylene again through decompressor and to control pressure be 2.0MPa, heat to 95 DEG C of constant temperature 5h, it is warming up to 100 DEG C, 18.1g(0.6%mol hypophosphorous acid ion is added again continuously in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, it is warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phosphinic acid sodium water solution 3169.3g, be equivalent to that ethylene absorption amount is 579.1g(theoretical amount 103.4%).
31P-NMR analyzes:
Diethyl phosphinic acid mol content: 98.1%
Ethyl phosphonous acid mol content: 0%
Phosphorous acid mol content: 0%
Other mol content: 1.9%
Take its aqueous solution 949.9g, add 2000g water, heated and stirred is to 90 DEG C, drip by 333.0g(0.5mol in 1.5h) the 20% Patent alum solution that is configured to of Patent alum and 1332g water, 90 DEG C of insulation 1h, filter, and with 2000L water washing 3 times, the filter cake obtained 130 DEG C is dried to constant weight, obtains aluminum diethylphosphinate: 374.6g, yield: 96.05%.
Embodiment 2: the preparation of one-component B ethyl phosphonous acid aluminum
By 1171.4g(10mol) 70% phosphorous acid, 9.1g(0.3%mol phosphorous acid) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane and 3.0g sodium borohydride, evacuate, replace 5 times with nitrogen, evacuate, it is filled with ethylene again through decompressor and to control pressure be 2.0MPa, heat to 90 DEG C of constant temperature 10h, and adding 18.1g(0.6%mol phosphorous acid continuously) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, it is warming up to 100 DEG C, insulation 1h, cooling emptying, obtain ethyl phosphonous acid solution 1487.5g, be equivalent to that ethylene absorption amount is 285.9g(theoretical amount 102.1%).
31P-NMR analyzes:
Ethyl phosphonous acid mol content: 98.8%
Phosphorous acid mol content: 0%
Other mol content: 1.2%
Take its solution 223.1g, add 1000g water, heated and stirred is to 90 DEG C, drip by 333.0g(0.5mol in 1.5h) the 20% Patent alum solution that is configured to of Patent alum and 1332g water, 90 DEG C of insulation 1h, filter, and with 1000L water washing 3 times, the filter cake obtained 130 DEG C is dried to constant weight, obtains ethyl phosphonous acid aluminum: 179.0g, yield: 93.98%.
Embodiment 3: the preparation of one-component C aluminium phosphite
1080g, 20wt%(1.0mol being instilled in 1110.0g, 20wt% (0.33mol) aluminum sulfate aqueous solution 1h) constant temperature is in the five hydration sodium phosphite aqueous solutions of 80 DEG C, filter, the 1000ml water washing three times of gained filter cake, obtains aluminium phosphite 94.27g, yield: 95.22%.
Embodiment 4:
Prepare aluminum diethylphosphinate with embodiment 1,5000g aluminum diethylphosphinate, 0.98g ethyl phosphonous acid aluminum are added high mixer and mixes 30 minutes, obtains polymeric additive compositions.
Wherein, ethyl phosphonous acid aluminum content is the 0.02wt%(mass fraction accounting for total content, lower same).
Embodiment 5:
5000g aluminum diethylphosphinate, 5.0g ethyl phosphonous acid aluminum are added high mixer and mixes 30 minutes, obtains polymeric additive compositions.
Wherein, ethyl phosphonous acid aluminum content is 0.1wt%.
Embodiment 6:
5000g aluminum diethylphosphinate, 48.4g ethyl phosphonous acid aluminum are added high mixer and mixes 30 minutes, obtains polymeric additive compositions.
Wherein, ethyl phosphonous acid aluminum content is 0.96wt%.
Embodiment 7:
5000g aluminum diethylphosphinate, 250.0g ethyl phosphonous acid aluminum are added high mixer and mixes 30 minutes, obtains polymeric additive compositions.
Wherein, ethyl phosphonous acid aluminum content is 4.8wt%.
Embodiment 8:
5000g aluminum diethylphosphinate, 500.0g ethyl phosphonous acid aluminum are added high mixer and mixes 30 minutes, obtains polymeric additive compositions.
Wherein, ethyl phosphonous acid aluminum content is 9.1wt%.
Embodiment 9:
5000g ethyl-butyl phosphinic acid aluminum, 1200.0g ethyl phosphonous acid aluminum are added high mixer and mixes 30 minutes, obtains polymeric additive compositions.
Wherein, ethyl phosphonous acid aluminum content is 19.4wt%.
Embodiment 10:
With embodiment 1, prepare 20wt% diethyl phosphinic acid sodium water solution, and addition 0.1wt%(ethyl phosphonous acid accounts for diethyl phosphinic acid mass percent in diethyl phosphinic acid sodium water solution, ethyl phosphonous acid sodium down together), reacts with theoretical amount 20wt% aluminum sulfate aqueous solution and prepares compositions of additives.
Ethyl phosphonous acid aluminum content is 0.1wt%.
Embodiment 11:
With embodiment 1, prepared 20wt% diethyl phosphinic acid sodium water solution, and in diethyl phosphinic acid sodium water solution, add the ethyl phosphonous acid sodium of 1.0wt%, react with theoretical amount 20wt% aluminum sulfate aqueous solution and prepare compositions of additives.
Ethyl phosphonous acid aluminum content 0.99wt%.
Embodiment 12:
With embodiment 1, prepared 20wt% diethyl phosphinic acid sodium water solution, and in diethyl phosphinic acid sodium water solution, add the ethyl phosphonous acid sodium of 10wt%, react with theoretical amount 20wt% aluminum sulfate aqueous solution and prepare compositions of additives.
Ethyl phosphonous acid aluminum content 9.1wt%.
Embodiment 13:
With embodiment 1, prepared 20wt% diethyl phosphinic acid sodium water solution, and in diethyl phosphinic acid sodium water solution, add the ethyl phosphonous acid sodium of 25wt%, react with theoretical amount 20wt% aluminum sulfate aqueous solution and prepare compositions of additives.
Ethyl phosphonous acid aluminum content 20wt%.
Embodiment 14:
By 1060.0g(10mol) a hydration sodium hypophosphite, 2.2g(0.01mol) five hydration sodium phosphite, 9.1g(0.3%mol hypophosphorous acid ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 3.0g sodium borohydride and 1500g water add in autoclave, evacuate, replace 3 times with nitrogen, evacuate, it is filled with ethylene again through decompressor and to control pressure be 2.0MPa, heat to 95 DEG C of constant temperature 5h, it is warming up to 100 DEG C, 18.1g(0.6%mol hypophosphorous acid ion is added again continuously in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, it is warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phosphinic acid sodium water solution 3173.6g, be equivalent to that ethylene absorption amount is 581.2g(theoretical amount 103.7%).
31P-NMR analyzes:
Diethyl phosphinic acid mol content: 99.9%
Ethyl phosphonous acid mol content: 0.1% (0.09wt%, is the mass content after aluminium salt for the conversion of mol content, lower same)
Phosphorous acid mol content: 0%
Take its aqueous solution 951.2g, add heating 2000g water, to 90 DEG C, drip by 333.7g(0.501mol in 1.5h) the 20% Patent alum solution that is configured to of Patent alum and 1333g water, 90 DEG C of insulation 1h, filter, and with 2000L water washing 3 times, the filter cake obtained 130 DEG C is dried to constant weight, obtains compositions of additives: 376.0g, yield (containing ethyl phosphonous acid aluminum, lower same): 96.31%.
Embodiment 15:
By 1060.0g(10mol) a hydration sodium hypophosphite, 21.6g(0.1mol) five hydration sodium phosphites, 9.1g(0.3%mol hypophosphorous acid ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 3.0g potassium borohydride and 1500g water add in autoclave, evacuate, replace 3 times with nitrogen, evacuate, it is filled with ethylene again through decompressor and to control pressure be 2.0MPa, heat to 87 DEG C of constant temperature 5h, it is warming up to 95 DEG C, 18.1g(0.6%mol hypophosphorous acid ion is added again continuously in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, it is warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phosphinic acid sodium water solution 3193.0g, be equivalent to that ethylene absorption amount is 581.2g(theoretical amount 103.3%).
31P-NMR analyzes:
Diethyl phosphinic acid mol content: 98.9%
Ethyl phosphonous acid mol content: 1.1% (0.97wt%)
Phosphorous acid mol content: 0%
Take its aqueous solution 957.9g, add 2000g water, heating is to 90 DEG C, drip by 339.7g(0.510mol in 1.5h) the 20% Patent alum solution that is configured to of Patent alum and 1359g water, 90 DEG C of insulation 1h, filter, and with 2000L water washing 3 times, the filter cake obtained 130 DEG C is dried to constant weight, obtains compositions of additives: 376.3g, yield: 95.56%.
Embodiment 16:
By 1060.0g(10mol) a hydration sodium hypophosphite, 108g(0.5mol) five hydration sodium phosphites, 9.1g(0.3%mol hypophosphorous acid ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 3.0g potassium borohydride and 1500g water add in autoclave, evacuate, replace 3 times with nitrogen, evacuate, it is filled with ethylene again through decompressor and to control pressure be 2.0MPa, heat to 87 DEG C of constant temperature 5h, it is warming up to 95 DEG C, 27.2g(0.9%mol hypophosphorous acid ion is added again continuously in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, it is warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phosphinic acid sodium water solution 3305.4g, be equivalent to that ethylene absorption amount is 598.1g(theoretical amount 104.2%).
31P-NMR analyzes:
Diethyl phosphinic acid mol content: 95.2%
Ethyl phosphonous acid mol content: 4.8% (4.2wt%)
Phosphorous acid mol content: 0%
Take its aqueous solution 991.0g, add 2000g water, heating is to 90 DEG C, drip by 366.3g(0.550mol in 1.5h) the 20% Patent alum solution that is configured to of Patent alum and 1465g water, 90 DEG C of insulation 1h, filter, and with 2000L water washing 3 times, the filter cake obtained 130 DEG C is dried to constant weight, obtains compositions of additives: 391.2g, yield: 95.64%. 409.5
Embodiment 17:
By 1060.0g(10mol) a hydration sodium hypophosphite, 216g(1.0mol) five hydration sodium phosphites, 9.1g(0.3%mol hypophosphorous acid ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 3.0g potassium borohydride and 1500g water add in autoclave, evacuate, replace 3 times with nitrogen, evacuate, it is filled with ethylene again through decompressor and to control pressure be 2.0MPa, heat to 87 DEG C of constant temperature 5h, it is warming up to 95 DEG C, 27.2g(0.9%mol hypophosphorous acid ion is added again continuously in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, it is warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phosphinic acid sodium water solution 3425.6g, be equivalent to that ethylene absorption amount is 610.3g(theoretical amount 103.8%).
31P-NMR analyzes:
Diethyl phosphinic acid mol content: 91.2%
Ethyl phosphonous acid mol content: 8.8% (7.8wt%)
Phosphorous acid mol content: 0%
Take its aqueous solution 1027.7g, add 2000g water, heating is to 90 DEG C, drip by 399.6g(0.600mol in 1.5h) the 20% Patent alum solution that is configured to of Patent alum and 1599g water, 90 DEG C of insulation 1h, filter, and with 2000L water washing 3 times, the filter cake obtained 130 DEG C is dried to constant weight, obtains compositions of additives: 409.2g, yield: 95.59%.
Embodiment 18:
By 1060.0g(10mol) a hydration sodium hypophosphite, 540.0g(2.5mol) five hydration sodium phosphites, 9.1g(0.3%mol hypophosphorous acid ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 3.0g potassium borohydride and 1500g water add in autoclave, evacuate, replace 3 times with nitrogen, evacuate, it is filled with ethylene again through decompressor and to control pressure be 2.0MPa, heat to 87 DEG C of constant temperature 5h, it is warming up to 95 DEG C, 32.3g(1.2%mol hypophosphorous acid ion is added again continuously in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, it is warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phosphinic acid sodium water solution 3804.0g, be equivalent to that ethylene absorption amount is 659.6g(theoretical amount 104.7%). 630
31P-NMR analyzes:
Diethyl phosphinic acid mol content: 80.8%
Ethyl phosphonous acid mol content: 19.2% (17.2wt%)
Phosphorous acid mol content: 0%
Take its aqueous solution 1141.2g, add 2000g water, heating is to 90 DEG C, drip by 499.5g(0.750mol in 1.5h) the 20% Patent alum solution that is configured to of Patent alum and 1998g water, 90 DEG C of insulation 1h, filter, and with 2000L water washing 3 times, the filter cake obtained 130 DEG C is dried to constant weight, obtains compositions of additives: 460.1g, yield: 94.82%.
Embodiment 19:
With embodiment 1, (0.1%mol is for accounting for diethyl phosphinic acid sodium mol percentage composition to add the sodium phosphite of 0.1mol% in diethyl phosphinic acid sodium water solution, lower same), compositions of additives is prepared with theoretical amount reacting aluminum sulfate, aluminium phosphite content 0.075wt%(aluminium phosphite quality accounts for phosphorous acid and aluminum diethylphosphinate gross mass percentage composition, lower same)
Embodiment 20:
With embodiment 1, diethyl phosphinic acid sodium water solution adds the sodium phosphite of 1.0mol%, prepare compositions of additives, aluminium phosphite content 0.75wt% with theoretical amount reacting aluminum sulfate.
Embodiment 21:
5000g aluminum diethylphosphinate, 1g aluminium phosphite are added high mixer and mix 30 minutes, obtains polymeric additive compositions.
Wherein, aluminium phosphite content is 0.02wt%.
Embodiment 22:
5000g aluminum diethylphosphinate, 5.0g aluminium phosphite are added high mixer and mix 30 minutes, obtains polymeric additive compositions.
Wherein, aluminium phosphite mass content is 0.10%.
Embodiment 23:
5000g aluminum diethylphosphinate, 45.0g aluminium phosphite are added high mixer and mix 30 minutes, obtains polymeric additive compositions.
Wherein, aluminium phosphite mass content is 0.89%.
Embodiment 24:
With embodiment 1, diethyl phosphinic acid sodium water solution adds the ethyl phosphonous acid sodium of 1mol% and the sodium phosphite of 1mol%, reacting with theoretical amount aluminum sulfate aqueous solution and prepare compositions of additives, ethyl phosphonous acid aluminum content 0.95wt%, aluminium phosphite content is 0.74wt%.
Embodiment 25:
5000g aluminum diethylphosphinate, 50g aluminium phosphite and 40g ethyl phosphonous acid aluminum are added high mixer mix 30 minutes, obtain polymeric additive compositions.
Wherein, ethyl phosphorous acid aluminum content is 0.98wt%, and phosphonous acid aluminum content is 0.78wt%.
Comparative example 1:
5000g aluminum diethylphosphinate and 60g aluminium phosphite are added high mixer mix 30 minutes, obtain polymeric additive compositions.
Wherein, aluminium phosphite content is 1.19wt%.
For each component of the additive of plastics in table 1 embodiment 1-25
By weight 10:50:30:10, the polymeric additive compositions of embodiment 1-25 and comparative example 1 gained is mixed that (embodiment 49 is that the blank sample without compositions of additives contrasts with PBT, glass, auxiliary agent at 230-260 DEG C, namely weight ratio is 0:50:30:10 mixing), extrude from Bitruder, prepare flame-proofed thermoplastic polymer in-mold moulding material, its combustibility and mechanical property are tested in sample preparation, record result referring to table 2 below:
Table 2 adds the flame-retardant PBT material property parameter table that polymeric additive compositions prepares
Continued 2:
Each performance test is undertaken by following standard:
1, hot strength: GB1040-1992 plastic tensile method for testing performance;
2, bending strength: GB9341-2000 Plastics-Oetermination of flexural properties method;
3, amount of deflection: GB9341-2000 Plastics-Oetermination of flexural properties method;
4, combustibility: UL94 Plastics Combustion performance test;
5, �� D(Screw Corrosion degree) determination: when 100t polymer molding compositions often processed by compounding combination unit, measure the diameter (before D and after D) of screw rod before and after producing, calculate after producing 100t polymer molding compositions, before the difference DELTA D=D of screw diameter after-D, �� D value is more big, represents that Screw Corrosion is more serious.
6, colourity testing standard:
Colourity test carries out on Color-Eye-7000A colour photometer (GretagMacbeth company), and concrete method of testing is:
1) resin is injection molded into the thick color plate of 2mm;
2) composition according to resin, the parameter such as calibrating that Lab value tester is set;
3) colour table being placed in test window, click " test " button, carry out the test of Lab value, system can show corresponding Lab value.
For this colorant of PBT, L-value is more big, and color is more white, is more easy to color matching.
Claims (10)
1. for a compositions of additives for polymer, including:
Component A:80wt%-99.99wt% has the dialkylphosphinic salts of structure shown in formula (I),
Wherein, R1, R2 is identical or different, is expressed as ethyl, propyl group and/or butyl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
Component B:0wt%-20wt% has the phostonic acid salt of structure shown in formula II,
(II)
Wherein, R3 is expressed as ethyl, propyl group and/or butyl; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(III)
Wherein, R3 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component B is 0wt%, component C is not 0wt%, and the summation of A, B and component C is always 100wt%.
2. a kind of compositions of additives for polymer as claimed in claim 1, it is characterised in that it comprises:
The component A of 95wt%-99.99wt%;
The component B of 0wt%-5wt%;
The component C of 0wt%-0.9wt%;
Component B is 0wt%, component C is not 0wt%, and the summation of A, B and component C is always 100wt%.
3. a kind of compositions of additives for polymer as claimed in claim 1, it is characterised in that described polymer is PBT, nylon, PPE, TPE, TPU, high-temperature nylon or epoxy resin, it is preferable that PBT, nylon or PPE.
One of 4. the preparation method of a kind of compositions of additives for polymer as claimed in claim 1, it is characterised in that as follows:
Method one:
A) hypophosphorous acid or its salt are added in a solvent, with olefine reaction under initiator and reaction promoter effect, the dialkyl phosphinic acid obtained or its saline solution, its solution metallizing thing reactant aqueous solution can prepare dialkylphosphinic salts;
B) adding phosphorous acid or its salt in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain phostonic acid or its saline solution, its solution metallizing thing reactant aqueous solution can prepare phostonic acid salt;
C) phosphorous acid or its salt metallizing thing are obtained by reacting phosphite;
D) product of step a and step b and/or step c gained mixed and get final product;
Wherein, described hypophosphites is sodium hypophosphite or potassium hypophosphite; Described phosphite is sodium phosphite or potassium phosphite;
Described metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe;
Or method two:
By miscible to dialkyl phosphinic acid or its saline solution and phostonic acid or its saline solution and/or phosphorous acid or its saline solution, then metallizing thing solution reaction and get final product.
5. the preparation method of a kind of compositions of additives for polymer as claimed in claim 4, it is characterised in that described solvent is water; Described initiator is azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator; Described alkene is one or both the mixture in ethylene and/or butylene.
6. the preparation method of a kind of compositions of additives for polymer as claimed in claim 4, it is characterised in that described reaction promoter is sodium borohydride or potassium borohydride.
7. as claimed in claim 1 a kind of compositions of additives for polymer as the purposes of fire retardant.
8. comprise a flame-proofed thermoplastic polymer in-mold moulding material for compositions of additives as claimed in claim 1, including the additive for polymer of 5-20 weight portion, the polymer of 50-70 weight portion or its mixture; Wherein, the additive for polymer includes:
Component A:80wt%-99.99wt% has the dialkylphosphinic salts of structure shown in formula (I),
Wherein, R1, R2 is identical or different, is expressed as ethyl, propyl group and/or butyl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
Component B:0wt%-20wt% has the phostonic acid salt of structure shown in formula II,
(II)
Wherein, R3 is expressed as ethyl, propyl group and/or butyl; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(III)
Wherein, R3 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component B is 0wt%, component C is not 0wt%, and the summation of A, B and component C is always 100wt%.
9. flame-proofed thermoplastic polymer in-mold moulding material as claimed in claim 8, it is characterised in that described polymer is polyester, nylon, high-temperature nylon, PPE, TPE, TPU or epoxy resin, it is preferable that polyester, nylon or PPE.
10. flame-proofed thermoplastic polymer in-mold moulding material as claimed in claim 8, it is characterised in that also include the glass fibre of 15-30 weight portion and other auxiliary agents of 1-5 weight portion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057649.6A CN105646938B (en) | 2014-10-29 | 2014-10-29 | A kind of compositions of additives and its preparation method for polymer and the flame-proofed thermoplastic polymer in-mold moulding material being made from it |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057649.6A CN105646938B (en) | 2014-10-29 | 2014-10-29 | A kind of compositions of additives and its preparation method for polymer and the flame-proofed thermoplastic polymer in-mold moulding material being made from it |
| CN201410592746.6A CN104371142B (en) | 2014-10-29 | 2014-10-29 | A kind of compositions of additives for polymer and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410592746.6A Division CN104371142B (en) | 2014-10-29 | 2014-10-29 | A kind of compositions of additives for polymer and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105646938A true CN105646938A (en) | 2016-06-08 |
| CN105646938B CN105646938B (en) | 2017-08-11 |
Family
ID=56488048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610057649.6A Active CN105646938B (en) | 2014-10-29 | 2014-10-29 | A kind of compositions of additives and its preparation method for polymer and the flame-proofed thermoplastic polymer in-mold moulding material being made from it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105646938B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976471A (en) * | 2018-06-27 | 2018-12-11 | 杭州本松新材料技术股份有限公司 | Fire retardant compound system and halogen-free flame-retardant resin based composites comprising it |
| CN111116988A (en) * | 2020-01-07 | 2020-05-08 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation method and application thereof |
| CN111303207A (en) * | 2020-04-09 | 2020-06-19 | 威海海润新材料科技有限公司 | Novel organic phosphide flame retardant and preparation method and application thereof |
| CN111320781A (en) * | 2020-03-13 | 2020-06-23 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation and application thereof |
| TWI788296B (en) * | 2016-09-15 | 2023-01-01 | 瑞士商克萊瑞特國際股份有限公司 | Flame retardant-stabilizer combination for thermoplastic polymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
| CN102171225A (en) * | 2008-12-18 | 2011-08-31 | 科莱恩金融(Bvi)有限公司 | Method for the production of alkylphosphonic acids, esters, and salts by oxidizing alkylphosphonous acids, and use thereof |
| WO2013083247A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
-
2014
- 2014-10-29 CN CN201610057649.6A patent/CN105646938B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
| CN102171225A (en) * | 2008-12-18 | 2011-08-31 | 科莱恩金融(Bvi)有限公司 | Method for the production of alkylphosphonic acids, esters, and salts by oxidizing alkylphosphonous acids, and use thereof |
| WO2013083247A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI788296B (en) * | 2016-09-15 | 2023-01-01 | 瑞士商克萊瑞特國際股份有限公司 | Flame retardant-stabilizer combination for thermoplastic polymers |
| CN108976471A (en) * | 2018-06-27 | 2018-12-11 | 杭州本松新材料技术股份有限公司 | Fire retardant compound system and halogen-free flame-retardant resin based composites comprising it |
| CN111116988A (en) * | 2020-01-07 | 2020-05-08 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation method and application thereof |
| CN111116988B (en) * | 2020-01-07 | 2020-11-20 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation method and application thereof |
| WO2021139073A1 (en) * | 2020-01-07 | 2021-07-15 | 威海海润新材料科技有限公司 | Organophosphorus compound flame retardant, and preparation method therefor and application thereof |
| JP2023504908A (en) * | 2020-01-07 | 2023-02-07 | ウェイハイ ヘレン ニュー－マテアリアル テック カンパニー リミテッド | Organophosphorus compound flame retardant and its production method and use |
| JP7356197B2 (en) | 2020-01-07 | 2023-10-04 | ウェイハイ ヘレン ニュー－マテアリアル テック カンパニー リミテッド | Organic phosphorus compound flame retardant and its manufacturing method and use |
| DE112020005224B4 (en) | 2020-01-07 | 2024-02-22 | Weihai Helen New-material Tech Co., Ltd. | PRODUCTION PROCESS FOR ORGANOPHOSPHATE FLAME RETARDANTS |
| CN111320781A (en) * | 2020-03-13 | 2020-06-23 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation and application thereof |
| CN111320781B (en) * | 2020-03-13 | 2021-09-07 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation and application thereof |
| CN111303207A (en) * | 2020-04-09 | 2020-06-19 | 威海海润新材料科技有限公司 | Novel organic phosphide flame retardant and preparation method and application thereof |
| CN111303207B (en) * | 2020-04-09 | 2023-04-25 | 威海海润新材料科技有限公司 | Organophosphorus flame retardant and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105646938B (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104371142B (en) | A kind of compositions of additives for polymer and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material | |
| CN104497504B (en) | A kind of compositions of additives for polymkeric substance and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material | |
| CN107189098B (en) | Additive for polymer, preparation method and application thereof, and flame-retardant polymer molding composition composed of additive | |
| CN105646938A (en) | Additive composition for polymers, preparation method thereof and flame-retardant thermoplastic polymer molding material composed of same | |
| CN103102367B (en) | Preparation method and application of dialkyl phosphinate with high density and large diameter | |
| CN105745278B (en) | Fire retardant resin composition and solar electrical energy generation module connection structural bodies | |
| EP3487957A1 (en) | Flame retardant mixtures, the production and the use thereof | |
| CN103172669B (en) | Monoalkyl/dialkyl phosphinate and preparation method thereof | |
| JP2017503870A (en) | Additive for polymer and production method thereof | |
| WO2018015252A1 (en) | Flame protection agent mixtures, their preparation and their use | |
| EP2563797A2 (en) | Method for producing mixtures of alkylphosphonous acid salts and dialkylphosphinic acid salts | |
| EP3487861A1 (en) | Diorganylphosphinic acid salts, method for the production thereof and the use thereof | |
| CN103172668A (en) | Monoalkyl/dialkyl phosphinate and preparation method thereof | |
| CN109851852A (en) | A kind of dialkylphosphinic salts composition of low-corrosiveness and its application | |
| CN109181295A (en) | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic and alkyl phosphite | |
| CN107207780A (en) | Flame-retardant mixture and its preparation | |
| JP2023504908A (en) | Organophosphorus compound flame retardant and its production method and use | |
| WO2024088091A1 (en) | Alkylphosphonous acid compound as well as preparation method therefor and use thereof | |
| CN114031779B (en) | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist | |
| WO2023280613A1 (en) | Sustainably produced dialkylphosphinic salts | |
| EP1122283B1 (en) | Flame-retardant polyketone resin composition and molded article | |
| CN108794804B (en) | The halogen-free flame-retardant system and its application of dialkyl dithio hypophosphites and nitrogenous compound collaboration | |
| CN108794805A (en) | Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of organic phosphite and nitrogenous compound collaboration and its application | |
| CN111303207B (en) | Organophosphorus flame retardant and preparation method and application thereof | |
| CN113429726B (en) | Preparation method of environment-friendly flame-retardant high impact polystyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190703 Address after: 519050 No. 177, No. 9 Petrochemical Road, Nanshui Town, Jinwan District, Zhuhai City, Guangdong Province Patentee after: ZHUHAI WANGO CHEMICAL Co.,Ltd. Address before: 510633 South China New Material Innovation Park G1 Building 1005, No. 31 Kefeng Road, Science City, Guangzhou High-tech Industrial Development Zone, Guangdong Province Patentee before: Guangzhou Kingsky Material Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| IP01 | Partial invalidation of patent right |
Commission number: 4W107629 Conclusion of examination: The patent is valid on the basis of claim 1-12 filed by the patentee on 28 September 2018. Decision date of declaring invalidation: 20190130 Decision number of declaring invalidation: 38769 Denomination of invention: Additive composition for polymer as well as preparation method for additive composition for polymer and flame retardant thermoplastic polymer molding material constituted by additive composition for polymer Granted publication date: 20170811 Patentee: ZHUHAI WANGO CHEMICAL Co.,Ltd. |
|
| IP01 | Partial invalidation of patent right |