CN105646938B - 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 - Google Patents
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 Download PDFInfo
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- CN105646938B CN105646938B CN201610057649.6A CN201610057649A CN105646938B CN 105646938 B CN105646938 B CN 105646938B CN 201610057649 A CN201610057649 A CN 201610057649A CN 105646938 B CN105646938 B CN 105646938B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000000654 additive Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000465 moulding Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims abstract description 14
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 229910052782 aluminium Inorganic materials 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 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 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 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
- 239000004677 Nylon Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 229910000765 intermetallic Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920001778 nylon Polymers 0.000 claims description 10
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 10
- 238000009938 salting Methods 0.000 claims description 10
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical group [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 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 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 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
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 150000001451 organic 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
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 239000005819 Potassium phosphonate Substances 0.000 claims 1
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 238000013329 compounding Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 3
- LYYXRDZATAMURV-UHFFFAOYSA-N ethylphosphonous acid Chemical compound CCP(O)O LYYXRDZATAMURV-UHFFFAOYSA-N 0.000 description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 29
- 239000004411 aluminium Substances 0.000 description 28
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical class CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 24
- 239000011734 sodium Substances 0.000 description 21
- 229910052708 sodium Inorganic materials 0.000 description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 20
- 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 15
- 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
- -1 salts Phosphate Chemical class 0.000 description 13
- 230000036571 hydration Effects 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 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
- 239000005977 Ethylene Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 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 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YUZPWHTZJLNXTL-UHFFFAOYSA-N [Na].CCP(O)O Chemical compound [Na].CCP(O)O YUZPWHTZJLNXTL-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000206 moulding compound Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 238000001035 drying Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YTMGLVBZNZLLIF-UHFFFAOYSA-N C(C)P(O)(O)O Chemical compound C(C)P(O)(O)O YTMGLVBZNZLLIF-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- FLKMXXYHGGVEPX-UHFFFAOYSA-N [K].OP(O)O Chemical compound [K].OP(O)O FLKMXXYHGGVEPX-UHFFFAOYSA-N 0.000 description 1
- BFBBORWYMUBDMS-UHFFFAOYSA-N [Na].C(C)P(O)=O Chemical compound [Na].C(C)P(O)=O BFBBORWYMUBDMS-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002947 alkylene 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
- SPWAXFLJYHRRJL-UHFFFAOYSA-N butyl(ethyl)phosphinic acid Chemical class CCCCP(O)(=O)CC SPWAXFLJYHRRJL-UHFFFAOYSA-N 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
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010452 phosphate 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000003825 pressing Methods 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
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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 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.Including：Component A：80wt% 99.99wt%'s has formula（I）The dialkylphosphinic salts of shown structure, component B：0wt% 20wt% have formula（Ⅱ）The phostonic acid salt of shown structure；Component C：0wt% 0.9wt% have formula（Ⅲ）The phosphite of shown structure；It is 0wt% when component B, C is different, and the summation of A, B and component C is always 100wt%.The additive application of the present invention is in polymer, flame-retardant polymer is greatly reduced to compounding combination unit Screw Corrosion degree, also reduced while reduction equipment processing cost in process and frequently change the energy and artificial loss caused by screw rod, and to put part whiteness by the polymer that extrusion molding is obtained and be better than the polymer that conventional dialkylphosphinic salts are modified and put part.
Description
The application is Application No. 201410592746.6, and the applying date is 2014-10-29, and invention and created name is " a kind of
Point of compositions of additives and its preparation method and the flame-proofed thermoplastic polymer in-mold moulding material that is made from it for polymer "
Case application.
Technical field
The present invention relates to a kind of compositions of additives for polymer, and in particular to one kind contains phostonic acid salt
And/or the dialkylphosphinic salts and its preparation method and the flame-proofed thermoplastic polymer in-mold plastic that is made from it of phosphite
Material.
Background technology
Dialkylphosphinic salts, are widely used as fire retardant, it is known that it can be synthesized by different methods.Such as patent
DE4430932 discloses two substitution metal phosphinates and is used as fire retardant in polyester, and DE19910232, US6248921 two is specially
Profit discloses a kind of preparation method of two substitutions metal phosphinate.United States Patent (USP) US6359171B1 discloses a kind of dialkyl group
The preparation method of phosphinic acids aluminium, this method synthesizes monoalkyl phosphonate using yellow phosphorus first, then triggers second using free radical
Hydrolyzed after alkylene it is sour after with aluminium salt reaction obtain dialkyl phosphinic acid aluminium fire retardant.
Aluminum diethylphosphinate is a kind of thermally-stabilised high, novel halogen-free flame-retardant agent of excellent fireproof performance.But actually should
Found with middle, the flame-retardant polymer moulding compound added with aluminum diethylphosphinate in process, is filled to compounding combination
The screw rod put can bring the corrosion of especially severe, and ambient polymer is damaged, and can especially cause the degraded of polymer.
Be primarily due to the dialkyl phosphinic acid that dialkyl phosphinic acid aluminium is ionized under the high temperature conditions has selection to metal ion
Property complexing, particularly to nickel, chromium of stainless steel clock etc. have higher selectivity so that in dialkylphosphinic salts fire-retardant
There is heavy corrosion to screw rod in Polymer Processing.We also found under study for action, corrosivity of the dialkylphosphinic salts to screw rod
Become even more serious with the growth of its alkyl chain.In actual applications it was also found that added with aluminum diethylphosphinate
Flame-retardant polymer put part whiteness and be short of.
We are mixed into part phostonic acid salt and/or a small amount of sub- phosphine by the discovery of research in dialkylphosphinic salts
Hydrochlorate, can largely mitigate the flame-retardant polymer moulding compound added with dialkylphosphinic salts in process
In the corrosion of screw rod is combined the unit to compounding, and on other performances of flame-retardant polymer almost without influence.
Patent CN103154110 is disclosed and the work that 1-80% phosphinates play stabilizer is mixed into dialkylphosphinic salts
With, it has been found that because the heat decomposition temperature of aluminium phosphite is relatively low, and during engineering plastics high temperature extrusion processing（Big portion
Division of labor engineering plastics processing temperature is above 200 DEG C）Easily thermally decomposed, it, which is decomposed, can produce the chance spontaneously inflammable hypertoxic phosphatization of air
Hydrogen other, we have discovered that its content is more beneficial for corrosion resistance, stability and its security less than 1%.
We also found by research simultaneously is mixed into part phostonic acid salt and/or a small amount of sub- in dialkylphosphinic salts
Phosphate so that the flame-retardant polymer moulding compound product whiteness added with dialkylphosphinic salts is more preferably.
The content of the invention
In order to solve the whiteness and its moulding compound of the flame-retardant polymer added with dialkylphosphinic salts processed
The problem of corrosion of screw rod is combined the unit to compounding in journey, it is an object of the invention to provide one kind in dialkylphosphinic salts
Compositions of additives containing phostonic acid salt and/or phosphite structure and the flame-proofed thermoplastic polymer in-mold being made from it
Moulding material.The additive application is small to compounding combination unit Screw Corrosion degree in process in polymer, to surrounding
Polymer damage degree is small, and obtained flame-retardant polymer molding compositions product whiteness is more preferable, and to other property of flame-retardant polymer
Can be almost without influence.
Another object of the present invention is to provide the above-mentioned use that a kind of technological process is simple, reaction time is short, gross production rate is high
In the preparation method of the compositions of additives of polymer.
The present invention is achieved by the following technical solutions：
A kind of compositions of additives for polymer, including：
Component A：80wt%-99.99wt%'s has formula（I）The dialkylphosphinic salts of shown structure,
Wherein, R1, R2It is identical or different, it is expressed as ethyl, propyl group and/or butyl；
M is Mg, Ca, Al, Zn, Fe；
M is 2 to 3；
Component B：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（Ⅱ）
Wherein, R3It is expressed as ethyl, propyl group and/or butyl；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
Component C：0wt%-0.9wt% has formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R3It is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
It is 0wt% when component B, C is different, and the summation of A, B and component C is always 100wt%.
It is preferred that, for the compositions of additives of polymer, it is included：
95wt%-99.99wt% component A；
0wt%-5wt% component B；
0wt%-0.9wt% component C；
It is 0wt% when component B, C is different, and the summation of A, B and component C is always 100wt%.
The polymer be PBT, nylon, PPE, TPE, TPU, high-temperature nylon or epoxy resin, preferably PBT, nylon or
PPE。
A kind of preparation method of the above-mentioned 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, are obtained
Dialkyl phosphinic acid or its salting liquid, its solution can prepare dialkylphosphinic salts with metallic compound reactant aqueous solution；
b）Phosphorous acid or its salt are added in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain alkane
Base phosphonous acid or its salting liquid, its solution can prepare phostonic acid salt with metallic compound reactant aqueous solution；
c）Phosphorous acid or its salt are obtained into phosphite with metallic compound reaction；
d）Product obtained by step a and step b and/or step c is mixed and produced；
Wherein, the hypophosphites is sodium hypophosphite or potassium hypophosphite；The phosphite is sodium phosphite or phosphorous acid
Potassium；
The metallic compound is Mg, Ca, Al, Zn, Fe metallic compound；
Or method two：
Dialkyl phosphinic acid or its salting liquid are mixed with phostonic acid or its salting liquid and/or phosphorous acid or its salting liquid
It is molten, then produced with metal compound solution reaction.
The solvent is water；The initiator is azo-initiator, organic peroxide evocating agent or inorganic peroxygen
Thing initiator；The alkene is the mixture of one or both of ethene and/or butylene.
Described reaction promoter is sodium borohydride or potassium borohydride.
A kind of compositions of additives for polymer of the present invention as fire retardant purposes.
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 parts by weight, the polymer of 50-70 parts by weight or its mixture；Wherein, for polymer
Additive include：
Component A：80wt%-99.99wt%'s has formula（I）The dialkylphosphinic salts of shown structure,
Wherein, R1, R2It is identical or different, it is expressed as ethyl, propyl group and/or butyl；
M is Mg, Ca, Al, Zn, Fe；
M is 2 to 3；
Component B：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（Ⅱ）
Wherein, R3It is expressed as ethyl, propyl group and/or butyl；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
Component C：0wt%-0.9wt% has formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R3It is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
It is 0wt% when component B, C is different, and the summation of A, B and component C is always 100wt%.
The polymer is polyester, nylon, high-temperature nylon, PPE, TPE, TPU or epoxy resin, preferably polyester, nylon or
PPE。
Flame-proofed thermoplastic polymer in-mold moulding material of the present invention, includes the glass fibre and 1-5 of 15-30 parts by weight
Other auxiliary agents of parts by weight.
The present invention compared with prior art, has the advantages that：
1）The dialkylphosphinic salts containing phostonic acid salt and/or phosphite structure that the present invention is prepared,
As the additive of flame-retardant polymer, the additive application is in polymer, in process, greatly reduces dialkyl group
Phosphinates, to compounding combination unit Screw Corrosion degree, reduces the same of equipment processing cost as the flame-retardant polymer of additive
When also reduce in process the energy and the artificial loss frequently changed caused by screw rod, the plastic additive has been widened significantly
Application in the market；
2）The dialkylphosphinic salts containing phostonic acid salt and/or phosphite structure that the present invention is prepared,
As the additive of flame-retardant polymer, the additive application is in polymer so that it is white that the polymer obtained by extrusion molding puts part
Degree puts part better than the polymer that conventional dialkylphosphinic salts are modified；
3）Additive preparation technology is simple, safety, and production cost is low, extremely with practicality.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiments.
Embodiment 1：The preparation of one-component A aluminum diethylphosphinates
By 1060.0g（10mol）One hydration sodium hypophosphite, 9.1g（0.3%mol hypophosphorous acid ions）1,1- di-t-butyl mistakes
Aoxidize -3,3,5- trimethyl-cyclohexanes, 3.0g sodium borohydrides and 1500g water to add in autoclave, evacuate, with nitrogen displacement 3 times,
Evacuate, then it is 2.0MPa to be filled with ethene and control pressure by pressure reducer, is heated to 95 DEG C of constant temperature 5h, is warming up to 100 DEG C, then 5h
It is interior continuously to add 18.1g（0.6%mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, heating
To 100 DEG C, 1h is incubated, cooling emptying obtains diethyl phosphinic acids sodium water solution 3169.3g, is equivalent to ethylene absorption amount
579.1g（The 103.4% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 98.1%
Ethyl phosphonous acid mol contents： 0%
Phosphorous acid mol contents： 0%
Other mol contents： 1.9%
Its aqueous solution 949.9g is taken, 2000g water is added, heating stirring is added dropwise by 333.0g to 90 DEG C in 1.5h
（0.5mol）The 20% Patent alum solution that Patent alum and 1332g water are configured to, 90 DEG C of insulation 1h, filtering,
And with 2000L water washings 3 times, the 130 DEG C of drying of obtained filter cake obtain aluminum diethylphosphinate to constant weight：374.6g, yield：
96.05%。
Embodiment 2：The preparation of one-component B ethyl phosphonous acid aluminium
By 1171.4g（10mol）70% phosphorous acid, 9.1g（0.3%mol phosphorous acid）1,1- di-tert-butyl peroxide -3,3,
5- trimethyl-cyclohexanes and 3.0g sodium borohydrides, are evacuated, and with nitrogen displacement 5 times, are evacuated, then be filled with ethene by pressure reducer and control
Pressing pressure is 2.0MPa, is heated to 90 DEG C of constant temperature 10h, and continuously adding 18.1g（0.6%mol phosphorous acid）1,1- di-t-butyls
Peroxidating -3,3,5- trimethyl-cyclohexanes are warming up to 100 DEG C, are incubated 1h, and cooling emptying obtains ethyl phosphonous acid solution
1487.5g, is 285.9g equivalent to ethylene absorption amount（The 102.1% of theoretical amount）.
31P-NMR is analyzed：
Ethyl phosphonous acid mol contents： 98.8%
Phosphorous acid mol contents： 0%
Other mol contents： 1.2%
Its solution 223.1g is taken, 1000g water is added, heating stirring is added dropwise by 333.0g to 90 DEG C in 1.5h
（0.5mol）The 20% Patent alum solution that Patent alum and 1332g water are configured to, 90 DEG C of insulation 1h, filtering,
And with 1000L water washings 3 times, the 130 DEG C of drying of obtained filter cake obtain ethyl phosphonous acid aluminium to constant weight：179.0g, yield：
93.98%。
Embodiment 3：The preparation of one-component C aluminium phosphites
By 1110.0g, 20wt% (0.33mol) aluminum sulfate aqueous solutions 1h is interior to instill 1080g, 20wt%（1.0mol）Constant temperature is
In 80 DEG C of the five hydration sodium phosphite aqueous solution, filtering, gained filter cake 1000ml water washings three times obtain aluminium phosphite
94.27g, yield：95.22%.
Embodiment 4：
Aluminum diethylphosphinate is made in be the same as Example 1, and 5000g aluminum diethylphosphinates, 0.98g ethyl phosphonous acid aluminium are added
Enter high mixer to mix 30 minutes, obtain polymeric additive composition.
Wherein, ethyl phosphonous acid aluminium content is 0.02wt%（The mass fraction of total content is accounted for, similarly hereinafter）.
Embodiment 5：
5000g aluminum diethylphosphinates, 5.0g ethyl phosphonous acid aluminium are added high mixer and mixed 30 minutes, polymer is obtained
Compositions of additives.
Wherein, ethyl phosphonous acid aluminium content is 0.1wt%.
Embodiment 6：
5000g aluminum diethylphosphinates, 48.4g ethyl phosphonous acid aluminium are added high mixer and mixed 30 minutes, is polymerize
Thing compositions of additives.
Wherein, ethyl phosphonous acid aluminium content is 0.96wt%.
Embodiment 7：
5000g aluminum diethylphosphinates, 250.0g ethyl phosphonous acid aluminium are added high mixer and mixed 30 minutes, is polymerize
Thing compositions of additives.
Wherein, ethyl phosphonous acid aluminium content is 4.8wt%.
Embodiment 8：
5000g aluminum diethylphosphinates, 500.0g ethyl phosphonous acid aluminium are added high mixer and mixed 30 minutes, is polymerize
Thing compositions of additives.
Wherein, ethyl phosphonous acid aluminium content is 9.1wt%.
Embodiment 9：
5000g ethyl-butyl phosphinic acids aluminium, 1200.0g ethyl phosphonous acid aluminium are added high mixer and mixed 30 minutes, is obtained
Polymeric additive composition.
Wherein, ethyl phosphonous acid aluminium content is 19.4wt%.
Embodiment 10：
Be the same as Example 1, is made 20wt% diethyl phosphinic acids sodium water solutions, and add in diethyl phosphinic acids sodium water solution
Enter 0.1wt%（Ethyl phosphonous acid accounts for diethyl phosphinic acids mass percent, similarly hereinafter）Ethyl phosphonous acid sodium, with theoretical amount 20wt%
Aluminum sulfate aqueous solution reaction prepares compositions of additives.
Ethyl phosphonous acid aluminium content is 0.1wt%.
Embodiment 11：
Be the same as Example 1, is made 20wt% diethyl phosphinic acids sodium water solutions, and add in diethyl phosphinic acids sodium water solution
Enter 1.0wt% ethyl phosphonous acid sodium, compositions of additives is prepared with the reaction of theoretical amount 20wt% aluminum sulfate aqueous solutions.
Ethyl phosphonous acid aluminium content 0.99wt%.
Embodiment 12：
Be the same as Example 1, is made 20wt% diethyl phosphinic acids sodium water solutions, and add in diethyl phosphinic acids sodium water solution
Enter 10wt% ethyl phosphonous acid sodium, compositions of additives is prepared with the reaction of theoretical amount 20wt% aluminum sulfate aqueous solutions.
Ethyl phosphonous acid aluminium content 9.1wt%.
Embodiment 13：
Be the same as Example 1, is made 20wt% diethyl phosphinic acids sodium water solutions, and add in diethyl phosphinic acids sodium water solution
Enter 25wt% ethyl phosphonous acid sodium, compositions of additives is prepared with the reaction of theoretical amount 20wt% aluminum sulfate aqueous solutions.
Ethyl phosphonous acid aluminium content 20wt%.
Embodiment 14：
By 1060.0g（10mol）One hydration sodium hypophosphite, 2.2g（0.01mol）Five hydration sodium phosphites, 9.1g（0.3%
Mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, 3.0g sodium borohydrides and 1500g water are added
In autoclave, evacuate, with nitrogen displacement 3 times, evacuate, then ethene is filled with by pressure reducer and control pressure is 2.0MPa, heating
To 95 DEG C of constant temperature 5h, 100 DEG C are warming up to, then continuously 18.1g is added in 5h（0.6%mol hypophosphorous acid ions）1,1- di-t-butyl mistakes
- 3,3,5- trimethyl-cyclohexanes are aoxidized, 100 DEG C are warming up to, 1h is incubated, cooling emptying obtains diethyl phosphinic acids sodium water solution
3173.6g, is 581.2g equivalent to ethylene absorption amount（The 103.7% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 99.9%
Ethyl phosphonous acid mol contents：0.1% (0.09wt% is that the conversion of mol contents is that quality after aluminium salt contains
Amount, similarly hereinafter)
Phosphorous acid mol contents： 0%
Its aqueous solution 951.2g is taken, heating 2000g water is added, to 90 DEG C, is added dropwise in 1.5h by 333.7g
（0.501mol）The 20% Patent alum solution that Patent alum and 1333g water are configured to, 90 DEG C of insulation 1h, mistake
Filter, and with 2000L water washings 3 times, 130 DEG C of obtained filter cake is dried to constant weight, obtains compositions of additives：376.0g, yield
(aluminium of phosphonous acid containing ethyl, similarly hereinafter)：96.31%.
Embodiment 15：
By 1060.0g（10mol）One hydration sodium hypophosphite, 21.6g（0.1mol）Five hydration sodium phosphites, 9.1g（0.3%
Mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, 3.0g potassium borohydrides and 1500g water are added
In autoclave, evacuate, with nitrogen displacement 3 times, evacuate, then ethene is filled with by pressure reducer and control pressure is 2.0MPa, heating
To 87 DEG C of constant temperature 5h, 95 DEG C are warming up to, then continuously 18.1g is added in 5h（0.6%mol hypophosphorous acid ions）1,1- di-t-butyl mistakes
- 3,3,5- trimethyl-cyclohexanes are aoxidized, 100 DEG C are warming up to, 1h is incubated, cooling emptying obtains diethyl phosphinic acids sodium water solution
3193.0g, is 581.2g equivalent to ethylene absorption amount（The 103.3% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 98.9%
Ethyl phosphonous acid mol contents： 1.1%(0.97wt%)
Phosphorous acid mol contents： 0%
Its aqueous solution 957.9g is taken, 2000g water is added, is heated to 90 DEG C, is added dropwise in 1.5h by 339.7g
（0.510mol）The 20% Patent alum solution that Patent alum and 1359g water are configured to, 90 DEG C of insulation 1h, mistake
Filter, and with 2000L water washings 3 times, 130 DEG C of obtained filter cake is dried to constant weight, obtains compositions of additives：376.3g, yield：
95.56%。
Embodiment 16：
By 1060.0g（10mol）One hydration sodium hypophosphite, 108g（0.5mol）Five hydration sodium phosphites, 9.1g（0.3%
Mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, 3.0g potassium borohydrides and 1500g water are added
In autoclave, evacuate, with nitrogen displacement 3 times, evacuate, then ethene is filled with by pressure reducer and control pressure is 2.0MPa, heating
To 87 DEG C of constant temperature 5h, 95 DEG C are warming up to, then continuously 27.2g is added in 5h（0.9%mol hypophosphorous acid ions）1,1- di-t-butyl mistakes
- 3,3,5- trimethyl-cyclohexanes are aoxidized, 100 DEG C are warming up to, 1h is incubated, cooling emptying obtains diethyl phosphinic acids sodium water solution
3305.4g, is 598.1g equivalent to ethylene absorption amount（The 104.2% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 95.2%
Ethyl phosphonous acid mol contents： 4.8%(4.2wt%)
Phosphorous acid mol contents： 0%
Its aqueous solution 991.0g is taken, 2000g water is added, is heated to 90 DEG C, is added dropwise in 1.5h by 366.3g
（0.550mol）The 20% Patent alum solution that Patent alum and 1465g water are configured to, 90 DEG C of insulation 1h, mistake
Filter, and with 2000L water washings 3 times, 130 DEG C of obtained filter cake is dried to constant weight, obtains compositions of additives：391.2g, yield：
95.64%。409.5
Embodiment 17：
By 1060.0g（10mol）One hydration sodium hypophosphite, 216g（1.0mol）Five hydration sodium phosphites, 9.1g（0.3%
Mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, 3.0g potassium borohydrides and 1500g water are added
In autoclave, evacuate, with nitrogen displacement 3 times, evacuate, then ethene is filled with by pressure reducer and control pressure is 2.0MPa, heating
To 87 DEG C of constant temperature 5h, 95 DEG C are warming up to, then continuously 27.2g is added in 5h（0.9%mol hypophosphorous acid ions）1,1- di-t-butyl mistakes
- 3,3,5- trimethyl-cyclohexanes are aoxidized, 100 DEG C are warming up to, 1h is incubated, cooling emptying obtains diethyl phosphinic acids sodium water solution
3425.6g, is 610.3g equivalent to ethylene absorption amount（The 103.8% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 91.2%
Ethyl phosphonous acid mol contents： 8.8%(7.8wt%)
Phosphorous acid mol contents： 0%
Its aqueous solution 1027.7g is taken, 2000g water is added, is heated to 90 DEG C, is added dropwise in 1.5h by 399.6g
（0.600mol）The 20% Patent alum solution that Patent alum and 1599g water are configured to, 90 DEG C of insulation 1h, mistake
Filter, and with 2000L water washings 3 times, 130 DEG C of obtained filter cake is dried to constant weight, obtains compositions of additives：409.2g, yield：
95.59%。
Embodiment 18：
By 1060.0g（10mol）One hydration sodium hypophosphite, 540.0g（2.5mol）Five hydration sodium phosphites, 9.1g（0.3%
Mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, 3.0g potassium borohydrides and 1500g water are added
In autoclave, evacuate, with nitrogen displacement 3 times, evacuate, then ethene is filled with by pressure reducer and control pressure is 2.0MPa, heating
To 87 DEG C of constant temperature 5h, 95 DEG C are warming up to, then continuously 32.3g is added in 5h（1.2%mol hypophosphorous acid ions）1,1- di-t-butyl mistakes
- 3,3,5- trimethyl-cyclohexanes are aoxidized, 100 DEG C are warming up to, 1h is incubated, cooling emptying obtains diethyl phosphinic acids sodium water solution
3804.0g, is 659.6g equivalent to ethylene absorption amount（The 104.7% of theoretical amount）.630
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 80.8%
Ethyl phosphonous acid mol contents： 19.2%(17.2wt%)
Phosphorous acid mol contents： 0%
Its aqueous solution 1141.2g is taken, 2000g water is added, is heated to 90 DEG C, is added dropwise in 1.5h by 499.5g
（0.750mol）The 20% Patent alum solution that Patent alum and 1998g water are configured to, 90 DEG C of insulation 1h, mistake
Filter, and with 2000L water washings 3 times, 130 DEG C of obtained filter cake is dried to constant weight, obtains compositions of additives：460.1g, yield：
94.82%。
Embodiment 19：
Be the same as Example 1, adds 0.1mol% sodium phosphite in diethyl phosphinic acids sodium water solution（0.1%mol is to account for two
Ethylphosphinic acid sodium mol percentage compositions, similarly hereinafter）, compositions of additives, phosphorous acid are prepared with theoretical amount reacting aluminum sulfate
Aluminium content 0.075wt%（Aluminium phosphite quality accounts for phosphorous acid and aluminum diethylphosphinate gross mass percentage composition, similarly hereinafter）
Embodiment 20：
Be the same as Example 1, adds 1.0mol% sodium phosphite, with theoretical amount sulfuric acid in diethyl phosphinic acids sodium water solution
Reactive aluminum prepares compositions of additives, aluminium phosphite content 0.75wt%.
Embodiment 21：
5000g aluminum diethylphosphinates, 1g aluminium phosphites are added high mixer and mixed 30 minutes, polymeric additive is obtained
Composition.
Wherein, aluminium phosphite content is 0.02wt%.
Embodiment 22：
5000g aluminum diethylphosphinates, 5.0g aluminium phosphites are added high mixer and mixed 30 minutes, polymer addition is obtained
Agent composition.
Wherein, aluminium phosphite mass content is 0.10 %.
Embodiment 23：
5000g aluminum diethylphosphinates, 45.0g aluminium phosphites are added high mixer and mixed 30 minutes, polymer is obtained and adds
Plus agent composition.
Wherein, aluminium phosphite mass content is 0.89 %.
Embodiment 24：
Be the same as Example 1, adds 1mol% ethyl phosphonous acid sodium and 1mol% Asia in diethyl phosphinic acids sodium water solution
Sodium phosphate, reacts with theoretical amount aluminum sulfate aqueous solution and prepares compositions of additives, ethyl phosphonous acid aluminium content 0.95wt%,
Aluminium phosphite content is 0.74wt%.
Embodiment 25：
5000g aluminum diethylphosphinates, 50g aluminium phosphites and 40g ethyl phosphonous acid aluminium are added into high mixer and mix 30 points
Clock, obtains polymeric additive composition.
Wherein, ethyl phosphorous acid aluminium content is 0.98wt%, and phosphonous acid aluminium content is 0.78wt%.
Comparative example 1：
5000g aluminum diethylphosphinates and 60g aluminium phosphites are added into high mixer to mix 30 minutes, polymer addition is obtained
Agent composition.
Wherein, aluminium phosphite content is 1.19wt%.
It is used for each component of the additive of plastics in the embodiment 1-25 of table 1
By the polymeric additive composition of embodiment 1-25 and the gained of comparative example 1 230-260 DEG C with PBT, glass, help
Agent is by weight 10:50:30:(embodiment 49 is the blank sample contrast without compositions of additives, i.e. weight ratio for 10 mixing
For 0:50:30:10 mixing), extruded from Bitruder, flame-proofed thermoplastic polymer in-mold moulding material, sample preparation test is made
Its combustibility and mechanical property, measure result referring to table 2 below：
Flame-retardant PBT material property parameter table made from the addition polymeric additive composition of table 2
Continued 2：
Each performance test is carried out by following standard：
1st, tensile strength：GB1040-1992 plastic tensile method for testing performances；
2nd, bending strength：GB9341-2000 Plastics-Oetermination of flexural properties methods；
3rd, amount of deflection：GB9341-2000 Plastics-Oetermination of flexural properties methods；
4th, combustibility：UL94 Plastics Combustion performance tests；
5、ΔD（Screw Corrosion degree）Determination:When compounding combination unit often processes 100t polymer molding compositions, survey
The diameter of screw rod before and after fixed production（Before D and after D）, calculate after production 100t polymer molding compositions, the difference of screw diameter
Before Δ D=D after-D, Δ D values are bigger, represent that Screw Corrosion is more serious.
6th, colourity testing standard：
Colourity is tested in Color-Eye-7000A colour photometers（GretagMacbeth companies）It is upper to carry out, specific test side
Method is：
1）Resin is molded into the thick colour tables of 2mm；
2）According to the composition of resin, the parameters such as the measurement bore of Lab value testers are set；
3）Colour table is placed in test window, " test " button is clicked on, the test of Lab values is carried out, system can be shown accordingly
Lab values.
For this colorant of PBT, L values are bigger, and color is whiter, are more easy to color matching.
Claims (12)
1. a kind of compositions of additives for polymer, including：
Component A：80wt%-99.99wt%'s has formula（I）The dialkylphosphinic salts of shown structure,
Wherein, R1, R2It is identical or different, it is expressed as ethyl, propyl group and/or butyl；
M is Mg, Ca, Al, Zn, Fe；
M is 2 to 3；
Component B：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（Ⅱ）
Wherein, R3It is expressed as ethyl, propyl group and/or butyl；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
Component C：0.75wt%-0.9wt% has formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R3It is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
Component B is that 0wt%, component C are 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 is included：
95wt%-99.99wt% component A；
0wt%-5wt% component B；
0.75wt%-0.9wt% component C；
Component B is that 0wt%, component C are 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 the polymer is
PBT, nylon, PPE, TPE, TPU or epoxy resin.
4. a kind of compositions of additives for polymer as claimed in claim 3, it is characterised in that the polymer is
PBT, nylon or PPE.
5. the preparation method of a kind of compositions of additives for polymer as claimed in claim 1, it is characterised in that press
State one of method：
Method one：
a）Hypophosphorous acid or its salt are added in a solvent, with olefine reaction under initiator and reaction promoter effect, obtained dioxane
Base phosphinic acids or its salting liquid, its solution can prepare dialkylphosphinic salts with metallic compound reactant aqueous solution；
b）Phosphorous acid or its salt are added in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain alkyl sub-
Phosphonic acids or its salting liquid, its solution can prepare phostonic acid salt with metallic compound reactant aqueous solution；
c）Phosphorous acid or its salt are obtained into phosphite with metallic compound reaction；
d）Product obtained by step a and step b and/or step c is mixed and produced；
Wherein, the hypophosphites is sodium hypophosphite or potassium hypophosphite；The phosphite is sodium phosphite or potassium phosphite；
The metallic compound is Mg, Ca, Al, Zn, Fe metallic compound；
Or method two：
Dialkyl phosphinic acid or its salting liquid and phostonic acid or its salting liquid and/or phosphorous acid or its salting liquid is miscible,
Then produced with metal compound solution reaction.
6. the preparation method of a kind of compositions of additives for polymer as claimed in claim 5, it is characterised in that described
Solvent is water；The initiator is azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator；It is described
Alkene is the mixture of one or both of ethene and/or butylene.
7. the preparation method of a kind of compositions of additives for polymer as claimed in claim 5, it is characterised in that described
Reaction promoter be sodium borohydride or potassium borohydride.
8. a kind of compositions of additives for polymer as claimed in claim 1 is used as the purposes of fire retardant.
9. a kind of flame-proofed thermoplastic polymer in-mold moulding material comprising compositions of additives as claimed in claim 1, including 5-20
The additive for polymer of parts by weight, the polymer of 50-70 parts by weight or its mixture；Wherein, adding for polymer
Plus agent includes：
Component A：80wt%-99.99wt%'s has formula（I）The dialkylphosphinic salts of shown structure,
Wherein, R1, R2It is identical or different, it is expressed as ethyl, propyl group and/or butyl；
M is Mg, Ca, Al, Zn, Fe；
M is 2 to 3；
Component B：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（Ⅱ）
Wherein, R3It is expressed as ethyl, propyl group and/or butyl；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
Component C：0.75wt%-0.9wt% has formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R3It is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 2 to 3；
Component B is that 0wt%, component C are not 0wt%, and the summation of A, B and component C is always 100wt%.
10. flame-proofed thermoplastic polymer in-mold moulding material as claimed in claim 9, it is characterised in that the polymer be polyester,
Nylon, PPE, TPE, TPU or epoxy resin.
11. flame-proofed thermoplastic polymer in-mold moulding material as claimed in claim 10, it is characterised in that the polymer is poly-
Ester, nylon or PPE.
12. flame-proofed thermoplastic polymer in-mold moulding material as claimed in claim 9, it is characterised in that also including 15-30 parts by weight
Glass fibre and 1-5 parts by weight other auxiliary agents.
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| 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 |
| 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 |
| 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 |
| 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 |
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| CA2311675C (en) * | 1997-11-28 | 2009-03-17 | Clariant Gmbh | Method for producing salts of dialkylphosphinic acids |
| DE102008063668A1 (en) * | 2008-12-18 | 2010-07-01 | Clariant International Limited | Process for the preparation of alkylphosphonic acids, esters and salts by oxidation of alkylphosphonous acids and their use |
| DE102011120200A1 (en) * | 2011-12-05 | 2013-06-06 | Clariant International Ltd. | Flame retardant mixtures containing flame retardants and aluminum phosphites, process for their preparation and their use |
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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. |
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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. |