CN105085988A - Additive composition for polymers, preparation method of additive composition and flame-retardant thermoplastic polymer molding material containing additive composition - Google Patents
Additive composition for polymers, preparation method of additive composition and flame-retardant thermoplastic polymer molding material containing additive composition Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Abstract
The invention discloses an additive composition for polymers, a preparation method of the additive composition and a flame-retardant thermoplastic polymer molding material containing the additive composition. The additive composition comprises the following components: a component A: 80wt%-99.99wt% of dialkyl phosphinate with a structure represented by a formula (I) (shown in the specification); a component B: 0.001wt%-0.5wt% of chloride, wherein the weight content of chlorine element in the total additive is 60ppm-800ppm; a component C: 0wt%-20wt% of alkyl phosphinate with a structure represented by a formula (II) (shown in the specification); and a component D: 0wt%-0.9wt% of phosphinate with a structure represented by a formula (III) (shown in the specification). The weight contents of the components C and D are not 0wt% simultaneously, and the sum of the weight contents of the components A, B, C and D is always 100wt%. By applying the additive to the polymers, the degree of corrosion caused by flame-retardant polymers to screw rods of a mixing assembling device is greatly decreased, the machining cost of equipment is lowered, meanwhile, the losses on energy sources and labors caused by the frequent exchange of the screw rods during machining are reduced, and furthermore, the whiteness of extruded polymer workpieces is superior to that of conventional polymer workpieces modified by dialkyl phosphinate.
Description
The application is application number is 201410826125.X, and the applying date is 2014-12-26, and invention and created name is the divisional application of " a kind of compositions of additives for polymkeric substance 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 polymkeric substance, be specifically related to a kind of dialkylphosphinic salts containing chlorine element and 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, and known its synthesizes by diverse ways.Be used as fire retardant as patent DE4430932 discloses two replacement metal phosphinates at polyester, DE19910232, US6248921 two sections patent discloses the preparation method that a kind of two replace metal phosphinate.US Patent No. 6359171B1 discloses a kind of preparation method of dialkyl phosphinic acid aluminium, first the method adopts yellow phosphorus to synthesize monoalkyl phosphonate, then utilize free radical to cause to be hydrolyzed after vinylation sour after and aluminium reactant salt obtain dialkyl phosphinic acid aluminium fire retardant.
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, be added with the flame-retardant polymer moulding compound of aluminum diethylphosphinate in the course of processing, the corrosion of especially severe can be brought the screw rod of compounding combination unit, and ambient polymer is damaged, especially can cause the degraded of polymkeric substance.Major cause is that the dialkyl phosphinic acid that is ionized under the high temperature conditions due to dialkyl phosphinic acid aluminium is to metal ion selectively complexing, particularly to the nickel, chromium etc. of stainless steel clock, there is higher selectivity, make in flame-retardant polymer processing, have heavy corrosion to screw rod at dialkylphosphinic salts.We also find under study for action, and dialkylphosphinic salts becomes even more serious to the corrodibility of screw rod along with the growth of its alkyl chain.
We find in dialkylphosphinic salts, be mixed into part phostonic acid salt and/or a small amount of phosphinate by research, can alleviate to a great extent be added with dialkylphosphinic salts flame-retardant polymer moulding compound in the course of processing to the corrosion of compounding combination unit screw rod, and on other performances of flame-retardant polymer almost without impact.Patent CN103154110 discloses and in dialkylphosphinic salts, is mixed into 1-80% phosphinate plays stablizer, we find, because the heat decomposition temperature of aluminum phosphite is lower, and in engineering plastics (most of engineering plastics processing temperature is all higher than 200 DEG C) easily decomposes in the high temperature extrusion course of processing, its decomposition can produce meet air spontaneously inflammable hypertoxic phosphuret-(t)ed hydrogen other, we study and find that its content is more conducive to erosion resistance, stability and security thereof lower than 1%.
In addition, dialkylphosphinic salts is used in flame-retardant polymer as fire retardant, flame-retardant polymer color can be made obviously to turn to be yellow.And the increasing substantially of polymkeric substance whiteness, it is a large difficulty of industry always, as for this colorant of polyester, its goods whiteness value L(Lab method) in 80 ~ 95 scopes time, whiteness value L differs about 1 and with the naked eye can obviously distinguish, the whiteness value L (Lab method) of goods is improved 1-2 point, will be also larger technological breakthrough.Therefore, we find to be mixed into part Micro Amounts of Chlorine in dialkylphosphinic salts for thing and phostonic acid salt and/or a small amount of phosphite by further research simultaneously, can not only alleviate to a great extent be added with dialkylphosphinic salts flame-retardant polymer moulding compound in the course of processing to the corrosion of compounding combination unit screw rod, and making the flame-retardant polymer moulding compound flame-retardant polymer yellowish phenomenon being added with dialkylphosphinic salts can obtain very significantly improving, product whiteness is better.
Summary of the invention
In order to solve the whiteness of the flame-retardant polymer being added with dialkylphosphinic salts and its moulding compound in the course of processing to the problem of the corrosion of compounding combination unit screw rod, the object of the present invention is to provide a kind of compositions of additives containing chlorine element and phostonic acid salt and/or phosphite structure in dialkylphosphinic salts and consisting of flame-proofed thermoplastic polymer in-mold moulding material.This additive application is in polymkeric substance, little to compounding combination unit Screw Corrosion degree in the course of processing, little to ambient polymer degree of damage, obtained flame-retardant polymer molding compositions product whiteness is better, and on other performances of flame-retardant polymer almost without affecting.
Another object of the present invention is to provide the preparation method of the above-mentioned compositions of additives for polymkeric substance that a kind of technical process is simple, reaction time is short, overall yield is high.
The present invention is achieved by the following technical solutions:
For a compositions of additives for polymkeric substance, comprising:
The dialkylphosphinic salts with structure shown in formula (I) of component A:80wt%-99.99wt%,
Wherein, R1, R2 are identical or different, are expressed as H, C1-C6 alkyl or C6-C18 aryl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
B component: 0.001wt%-0.5wt% muriate, the weight content of chlorine element in total additive is 60-800ppm;
Component C: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 D:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(Ⅲ)
Wherein, R4 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C, D are 0wt% time different, and the summation of A, B, C and D component is always 100wt%.
Preferably, R1, R2 are expressed as ethyl, propyl group and/or butyl.
Preferably, the weight content of described chlorine element in total additive is 70-450ppm, and preferred weight content is
70-200ppm.
Described muriate is selected from one or more in chlorinated alkenes, sodium-chlor, Repone K, aluminum chloride, chlorine, hydrochloric acid, clorox, chloride coupling agent, chlorine-containing flame retardant, chloride tensio-active agent or PVC;
Described muriate also can be selected from 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, 2-Dichloroethyl ethylphosphinic acid salt, 1, 2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, one or more in chlorocyclohexyl phosphinates, described salt is sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
Described polymkeric substance is PBT, nylon, PPE, TPE, TPU or epoxy resin, preferred PBT, nylon or PPE.
One of the preparation method of a kind of compositions of additives for polymkeric substance of the present invention, as follows:
Method one:
A) Hypophosporous Acid, 50 or its salt and chlorinated alkenes is added in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain containing muriatic dialkyl phosphinic acid or its salts solution, its solution metallizing thing reactant aqueous solution can prepare containing muriatic dialkylphosphinic salts;
B) add phosphorous acid or its salt in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain phostonic acid or its salts 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 is mixed and get final product;
Wherein, described hypophosphite 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;
Described chlorinated alkenes is one or more in 1-vinylchlorid, 1,2-dichloroethene, chlorallylene, 4-chlorobutylene or chloro tetrahydrobenzene.
Or method two:
By dialkyl phosphinic acid or its salts solution metallizing thing solution reaction, obtain dialkyl hypophosphorous acid salt, then, after miscible with the aqueous solution of additive I, obtain containing muriatic dialkylphosphinic salts, then with phostonic acid or its salts solution and/or phosphorous acid or its salts solution miscible and get final product;
Wherein, described additive I is NaCl, KCl, AlCl
3, chlorine, hydrochloric acid, clorox, one or more in chloride coupling agent or chloride tensio-active agent;
Described additive I also can select 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, 2-Dichloroethyl ethylphosphinic acid salt, 1, 2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, one or more in chlorocyclohexyl phosphinates, described salt is sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
Described metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe.
Described dialkylphosphinic salts is dialkyl phosphinic acid sodium or dialkyl phosphinic acid potassium; Described phosphite is sodium phosphite or potassium phosphite.
Or method three:
By dialkyl phosphinic acid or its salts solution metallizing thing solution reaction, obtain dialkyl hypophosphorous acid salt, then with phostonic acid or its salts solution and/or phosphorous acid or its salts solution miscible, finally in product filtration procedure or washing process or drying course, add additive II and get final product;
Wherein, described additive II is NaCl, KCl, AlCl
3, chlorine-containing flame retardant, chloride coupling agent, one or more in chloride tensio-active agent or PVC.
Described additive II also can select 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, 2-Dichloroethyl ethylphosphinic acid salt, 1, 2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, one or more of chlorocyclohexyl phosphinates, described salt is sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
Or method four:
The raw material preparing dialkyl hypophosphorous acid salt containing chlorine element will be added in solvent, with olefine reaction under initiator and reaction promoter effect, obtain containing muriatic dialkyl phosphinic acid or its salts solution, its solution metallizing thing reactant aqueous solution can prepare containing muriatic dialkylphosphinic salts, and then with phostonic acid or its salts solution and/or phosphorous acid or its salts solution miscible, to obtain final product.
Wherein, 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 ethene and/or butylene; Described reaction promoter is sodium borohydride or POTASSIUM BOROHYDRIDE.
The invention discloses the purposes of above-mentioned a kind of compositions of additives for polymkeric substance as fire retardant.
The invention also discloses a kind of flame-proofed thermoplastic polymer in-mold moulding material comprising above-mentioned compositions of additives, comprise the additive for polymkeric substance of 5-20 weight part, the polymkeric substance of 50-70 weight part or its mixture; Wherein, the additive for polymkeric substance comprises:
The dialkylphosphinic salts with structure shown in formula (I) of component A:80wt%-99.99wt%,
Wherein, R1, R2 are identical or different, are expressed as H, C1-C6 alkyl or C6-C18 aryl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
B component: 0.001wt%-0.5wt% muriate, the weight content of chlorine element in total additive is 60-800ppm;
Component C: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 D:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(Ⅲ)
Wherein, R4 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C, D are 0wt% time different, and the summation of A, B, C and D component is always 100wt%.
Preferably, R1, R2 are expressed as ethyl, propyl group and/or butyl.
Preferably, the weight content of described chlorine element in total additive is 70-450ppm, and preferred weight content is 70-200ppm.
Described muriate is selected from one or more in chlorinated alkenes, sodium-chlor, Repone K, aluminum chloride, chlorine, hydrochloric acid, clorox, chloride coupling agent, chlorine-containing flame retardant, chloride tensio-active agent or PVC;
Described muriate also can be selected from 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, 2-Dichloroethyl ethylphosphinic acid salt, 1, 2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, one or more in chlorocyclohexyl phosphinates, described salt is sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
Described polymkeric substance is described polymkeric substance is PBT, nylon, PPE, TPE, TPU or epoxy resin, preferred PBT, nylon or PPE.
Flame-proofed thermoplastic polymer in-mold moulding material of the present invention, also comprises the glass fibre of 15-30 weight part and other auxiliary agents of 1-5 weight part.
The present invention compared with prior art, has following beneficial effect:
1) dialkylphosphinic salts containing chlorine element and phostonic acid salt and/or phosphite structure for preparing of the present invention, as the additive of flame-retardant polymer, this additive application is in polymkeric substance, in the course of processing, greatly reduce the flame-retardant polymer of dialkylphosphinic salts as additive to compounding combination unit Screw Corrosion degree, the energy and artificial loss that in the course of processing, frequent replacing screw rod causes is also reduced while reducing apparatus processing cost, and make the polymeric articles whiteness obtained through extrusion molding be better than the polymeric articles of conventional dialkylphosphinic salts modification, greatly widen this plastics additive range of application in the market,
2) simple, the safety of this additive preparation technology, production cost is low, very has practicality.
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
embodiment 1: the preparation of single-component A aluminum diethylphosphinate
By 636.0g(6mol) a hydration sodium hypophosphite, 5.5g(0.3%mol Hypophosporous Acid, 50 ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 1.8g sodium borohydride and 900g water add in autoclave, find time, with nitrogen replacement 3 times, find time, ethene is filled with again and control pressure is 2.0MPa by pressure reducer, be heated to 95 DEG C of constant temperature 5h, be warming up to 100 DEG C, 10.9g(0.6%mol Hypophosporous Acid, 50 ion is added continuously again in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, be warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phospho acid sodium water solution 1902.7g, be equivalent to that ethylene absorption amount is 348.5g(theoretical amount 103.7%).
31p-NMR analyzes:
Diethyl phospho acid mol content: 98.3%
Ethyl phosphonous acid mol content: 0%
Phosphorous acid mol content: 0%
Other mol content: 1.9%
Get its aqueous solution 951.4g, add 2000g water, heated and stirred to 90 DEG C, drip by 333.0g(0.5mol in 1.5h) 20% Patent alum solution that Patent alum and 1332g water are configured to, 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: 375.4g, yield: 96.26%.
embodiment 2: the preparation of single-component C 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-cyclohexane and 3.0g sodium borohydride, find time, with nitrogen replacement 5 times, find time, ethene is filled with again and control pressure is 2.0MPa by pressure reducer, be heated 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, be warming up to 100 DEG C, insulation 1h, cooling emptying, obtain ethyl phosphonous acid solution 1490.8g, be equivalent to that ethylene absorption amount is 289.2g(theoretical amount 103.3%).
31p-NMR analyzes:
Ethyl phosphonous acid mol content: 98.2%
Phosphorous acid mol content: 0%
Other mol content: 1.8%
Get its solution 223.6g, add 1000g water, heated and stirred to 90 DEG C, drip by 333.0g(0.5mol in 1.5h) 20% Patent alum solution that Patent alum and 1332g water are configured to, 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 aluminium: 174.8g, yield: 92.5%.
embodiment 3: the preparation of single-component D aluminum phosphite
By instillation 1080g, 20wt%(1.0mol in 1110.0g, 20wt% (0.33mol) aluminum sulfate aqueous solution 1h) constant temperature is in the five hydration sodium phosphite aqueous solution of 80 DEG C, filter, the 1000ml water washing three times of gained filter cake, obtains aluminum phosphite 90.8g, yield: 92.7%.
the preparation of embodiment 4-8: component A+ component B
By 2120.0g(20mol) sodium hypophosphite, 1320.0g(10mol) 50% phospho acid, 27.2g(0.3%mol Hypophosporous Acid, 50 ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane and 3000g water, add in autoclave, find time, with nitrogen replacement 3 times, find time, quantitatively be filled with chloro-alkenes, ethene is filled with again and control pressure is 1.8MPa by pressure reducer, be heated to 87 DEG C, constant temperature 5h, be heated to 95 DEG C, 54.4g(0.6%mol Hypophosporous Acid, 50 ion is added continuously again in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, be warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phospho acid sodium and diethyl phospho acid mixing solutions 8297.8g, be equivalent to that ethylene absorption amount is 1772.1g(theoretical amount 105.5%).
31p-NMR analyzes:
Diethyl phospho acid mol content: 96.8%
Ethyl-butyl phospho acid mol content: 2.1%
Ethylphosphinic acid mol content: 1.2
Other mol content: 0.9%
Get diethyl phospho acid sodium and diethyl phospho acid mixing solutions 829.7g, add 1600g water, be neutralized to neutrality with 30% sodium hydroxide solution, be heated 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 oven dry is to constant weight, obtain aluminum diethylphosphinate: 373.2g, yield: 95.7%.
According to above-mentioned steps, chloro-alkenes selects vinylchlorid respectively, 1, 2-Ethylene Dichloride, chlorallylene, 4-chlorobutylene or chloro tetrahydrobenzene substitute, component A+B can be prepared, wherein different according to its alkene, B component can be respectively: 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, 2-Dichloroethyl ethylphosphinic acid salt, 1, 2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, chlorocyclohexyl phosphinates etc., make in aluminum diethylphosphinate containing Micro Amounts of Chlorine element.Its component is as shown in the table:
Table 1. embodiment 4 ~ 8 mixture forms
embodiment 9 ~ 13: the preparation of component A+ component B
Prepare aluminum diethylphosphinate with embodiment 1, mix with the chlorine-containing compound shown in table 2, prepare component A+ B component mixture.
table 2. embodiment 9 ~ 13 mixture forms
embodiment 14: the preparation of component A+ component B
By 636.0g(6mol) a hydration sodium hypophosphite (content of Cl element is 960ppm), 5.5g(0.3%mol Hypophosporous Acid, 50 ion) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, 1.8g sodium borohydride and 900g water add in autoclave, find time, with nitrogen replacement 3 times, find time, ethene is filled with again and control pressure is 2.0MPa by pressure reducer, be heated to 95 DEG C of constant temperature 5h, be warming up to 100 DEG C, 10.9g(0.6%mol Hypophosporous Acid, 50 ion is added continuously again in 5h) 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethyl-cyclohexane, be warming up to 100 DEG C, insulation 1h, cooling emptying, obtain diethyl phospho acid sodium water solution 1904.6g, be equivalent to that ethylene absorption amount is 350.4g(theoretical amount 104.3%).
31p-NMR analyzes:
Diethyl phospho acid mol content: 98.0%
Ethyl phosphonous acid mol content: 0%
Phosphorous acid mol content: 0%
Other mol content: 2.0%
Get its aqueous solution 952.3g, add 2000g water, heated and stirred to 90 DEG C, drip by 333.0g(0.5mol in 1.5h) 20% Patent alum solution that Patent alum and 1332g water are configured to, 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: 372.5g, yield: 95.5%.
Cl content: 76ppm
embodiment 15 ~ 25: the preparation of composition
Mixed with embodiment 2 component C and/or embodiment 3 component D by the A+B mixture of embodiment 4 ~ 14, can obtain flame retardant composition, its component is as shown in table 3.
table 3.for the composition of the compositions of additives of polymkeric substance
embodiment 26: the preparation of composition
With embodiment 1, be prepared into aluminum diethylphosphinate slurries (theoretical dry weight 200g), add 2g ethyl phosphonous acid aluminium and 1g aluminum phosphite, stir, filter, filter twice with 600ml water washing, then wash with 0.2wt% aluminum chloride aqueous solution 600ml, filter, drying obtains flame retardant composition.
Wherein, ethyl phosphonous acid aluminium content is 0.98wt%, and aluminum phosphite content is 0.49wt%, content of Cl element: 98ppm.
comparative example 1 ~ 3: the preparation of comparative example composition
By embodiment 1 ~ 3(component A, C, D) mix mixing, can obtain composition, its component is as shown in continued 3:
continued 3. composition forms
embodiment 27-38 and comparative example 4-9: the preparation of flame-proofed thermoplastic polymer in-mold moulding material
By embodiment 15-26,4,6 and the polymeric additive composition of comparative example 1-3 gained mix by weight 10:50:30:10 with PBT, glass, auxiliary agent at 230-260 DEG C
(comparative example 4 is do not add the blank sample contrast of compositions of additives, and namely weight ratio is 0:50:30:10 mixing), extrude from Bitruder, obtained flame-proofed thermoplastic polymer in-mold moulding material, its combustionproperty and mechanical property are tested in sample preparation, record result and see table 4:
Table 4 adds the obtained flame-retardant PBT material property parameter table of polymeric additive composition
Continued 4:
each performance test is undertaken by following standard:
1, tensile strength: GB1040-1992 plastic tensile method for testing performance;
2, flexural strength: GB9341-2000 Plastics-Oetermination of flexural properties method;
3, amount of deflection: GB9341-2000 Plastics-Oetermination of flexural properties method;
4, combustionproperty: UL94 Plastics Combustion performance test;
5, Δ 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, Δ D value is larger, represents that Screw Corrosion is more serious.
6, colourity testing standard:
Colourity test is carried out on Color-Eye-7000A color measurement instrument (GretagMacbeth company), and concrete testing method is:
1) resin is injection molded into the thick colour table of 2mm;
2) according to the composition of resin, the parameters such as the calibrating of Lab value tester are set;
3) colour table is placed in test window, clicks " test " button, carry out the test of Lab value, system can show corresponding Lab value.
For this colorant of PBT, L value is larger, and color is whiter, is more convenient to color matching.
7, the examination criteria of cl content: prEN14582-2002 halogen detection method.
Claims (14)
1. for a compositions of additives for polymkeric substance, comprising:
The dialkylphosphinic salts with structure shown in formula (I) of component A:80wt%-99.99wt%,
Wherein, R1, R2 are identical or different, are expressed as H, C1-C6 alkyl or C6-C18 aryl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
B component: 0.001wt%-0.5wt% muriate, the weight content of chlorine element in total additive is 60-800ppm;
Component C: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 D:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(Ⅲ)
Wherein, R4 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C is 0wt%, component D is not 0wt%, and the summation of A, B, C and D component is always 100wt%.
2. a kind of compositions of additives for polymkeric substance as claimed in claim 1, it is characterized in that, R1, R2 are expressed as ethyl, propyl group and/or butyl.
3. a kind of compositions of additives for polymkeric substance as claimed in claim 1, it is characterized in that, the weight content of described chlorine element in total additive is 70-450ppm, and preferred weight content is 70-200ppm.
4. a kind of compositions of additives for polymkeric substance as claimed in claim 1, it is characterized in that, described muriate is selected from chlorinated alkenes, sodium-chlor, Repone K, aluminum chloride, chlorine, hydrochloric acid, clorox, chloride coupling agent, chlorine-containing flame retardant, chloride tensio-active agent, PVC, 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, 2-Dichloroethyl ethylphosphinic acid salt, 1, 2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, one or more in chlorocyclohexyl phosphinates.
5. a kind of compositions of additives for polymkeric substance as claimed in claim 1, it is characterized in that, described polymkeric substance is PBT, nylon, PPE, TPE, TPU or epoxy resin, preferred PBT, nylon or PPE.
One of 6. the preparation method of a kind of compositions of additives for polymkeric substance as claimed in claim 1, is characterized in that, as follows:
Method one:
A) Hypophosporous Acid, 50 or its salt and chlorinated alkenes is added in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain containing muriatic dialkyl phosphinic acid or its salts solution, its solution metallizing thing reactant aqueous solution can prepare containing muriatic dialkylphosphinic salts;
B) add phosphorous acid or its salt in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain phostonic acid or its salts 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 is mixed and get final product;
Wherein, described hypophosphite 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;
Described chlorinated alkenes is one or more in 1-vinylchlorid, 1,2-dichloroethene, chlorallylene, 4-chlorobutylene or chloro tetrahydrobenzene;
Or method two:
By dialkyl phosphinic acid or its salts solution metallizing thing solution reaction, obtain dialkyl hypophosphorous acid salt, then, after miscible with the aqueous solution of additive I, obtain containing muriatic dialkylphosphinic salts, then with phostonic acid or its salts solution and/or phosphorous acid or its salts solution miscible and get final product;
Wherein, described additive I is NaCl, KCl, AlCl
3, chlorine, hydrochloric acid, clorox, chloride coupling agent or chloride tensio-active agent, 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, one or more in 2-Dichloroethyl ethylphosphinic acid salt, 1,2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, chlorocyclohexyl phosphinates;
Described salt is sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
Described metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe.
Described dialkylphosphinic salts is dialkyl phosphinic acid sodium or dialkyl phosphinic acid potassium; Described phosphite is sodium phosphite or potassium phosphite;
Or method three:
By dialkyl phosphinic acid or its salts solution metallizing thing solution reaction, obtain dialkyl hypophosphorous acid salt, then with phostonic acid or its salts solution and/or phosphorous acid or its salts solution miscible, finally in product filtration procedure or washing process or drying course, add additive II and get final product;
Wherein, described additive II is NaCl, KCl, AlCl
3, chlorine-containing flame retardant, chloride coupling agent, chloride tensio-active agent, PVC, 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, one or more in 2-Dichloroethyl ethylphosphinic acid salt, 1,2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, chlorocyclohexyl phosphinates.
Described salt is sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
Or method four:
Add the raw material preparing dialkyl hypophosphorous acid salt containing chlorine element in a solvent, with olefine reaction under initiator and reaction promoter effect, obtain containing muriatic dialkyl phosphinic acid or its salts solution, its solution metallizing thing reactant aqueous solution can prepare containing muriatic dialkylphosphinic salts, and then with phostonic acid or its salts solution and/or phosphorous acid or its salts solution miscible, to obtain final product.
7. the preparation method of a kind of compositions of additives for polymkeric substance as claimed in claim 6, it is characterized 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 ethene and/or butylene; Described reaction promoter is sodium borohydride or POTASSIUM BOROHYDRIDE.
8. as claimed in claim 1 a kind of compositions of additives for polymkeric substance as the purposes of fire retardant.
9. comprise a flame-proofed thermoplastic polymer in-mold moulding material for compositions of additives as claimed in claim 1, comprise the additive for polymkeric substance of 5-20 weight part, the polymkeric substance of 50-70 weight part or its mixture; Wherein, the additive for polymkeric substance comprises:
The dialkylphosphinic salts with structure shown in formula (I) of component A:80wt%-99.99wt%,
Wherein, R1, R2 are identical or different, are expressed as H, C1-C6 alkyl or C6-C18 aryl;
M is Mg, Ca, Al, Zn, Fe;
M is 2 to 4;
B component: 0.001wt%-0.5wt% muriate, the weight content of chlorine element in total additive is 60-800ppm;
Component C: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 D:0wt%-0.9wt% has the phosphite of structure shown in formula III;
(Ⅲ)
Wherein, R4 is expressed as H; M is Mg, Ca, Al, Zn, Fe; M is 1 to 4;
Component C is 0wt%, component D is not 0wt%, and the summation of A, B, C and D component is always 100wt%.
10. flame-proofed thermoplastic polymer in-mold moulding material as claimed in claim 9, it is characterized in that, R1, R2 are expressed as ethyl, propyl group and/or butyl.
11. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 9, is characterized in that, the weight content of described chlorine element in total additive is 70-450ppm, and preferred weight content is 70-200ppm.
12. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 9, it is characterized in that, described muriate is selected from chlorinated alkenes, sodium-chlor, Repone K, aluminum chloride, chlorine, hydrochloric acid, clorox, chloride coupling agent, chlorine-containing flame retardant, chloride tensio-active agent, PVC, 1-chloroethylethyl phosphinates, 1-chloroethyl phosphinates, 1, 2-Dichloroethyl ethylphosphinic acid salt, 1, 2-Dichloroethyl phosphinates, 3-chloropropyl propylphosphinic acid salt, 3-chloropropyl phosphinates, 4-chlorobutyl ethylphosphinic acid salt, 4-chlorobutyl butyl phosphinates, 4-chlorobutyl phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, one or more in chlorocyclohexyl phosphinates.
13. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 9, is characterized in that, described polymkeric substance is described polymkeric substance is PBT, nylon, PPE, TPE, TPU or epoxy resin, preferred PBT, nylon or PPE.
14. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 9, is characterized in that, also comprise the glass fibre of 15-30 weight part and other auxiliary agents of 1-5 weight part.
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CN111825883A (en) * | 2019-04-15 | 2020-10-27 | 黎杰 | Metal complex salts of polydialkylphosphinic acids and/or mixtures thereof, and use thereof |
TWI787301B (en) * | 2017-07-14 | 2022-12-21 | 瑞士商克萊瑞特國際股份有限公司 | Additive mixtures for plastics, laser-markable polymer compositions comprising them and the use thereof |
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CN104371142B (en) * | 2014-10-29 | 2016-07-13 | 广州金凯新材料有限公司 | 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) * | 2014-12-26 | 2016-03-30 | 肖群 | A kind of compositions of additives for polymkeric substance and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material |
DE102016213281A1 (en) | 2016-07-20 | 2018-01-25 | Clariant Plastics & Coatings Ltd | Flame retardant mixtures, their preparation and their use |
CN107141511B (en) * | 2017-05-25 | 2019-07-12 | 广州铂钡信息科技有限公司 | A kind of additive and preparation method thereof for polymer |
CN107417977B (en) * | 2017-07-19 | 2019-07-12 | 广州铂钡信息科技有限公司 | A kind of additive and preparation method thereof for polymer |
CN111662323A (en) * | 2019-03-07 | 2020-09-15 | 黎杰 | Dialkyl phosphinic acid-alkyl phosphorous acid metal composite salt, preparation method and application thereof |
CN114085422B (en) * | 2021-11-30 | 2023-05-23 | 广东宇星阻燃新材股份有限公司 | Preparation method of inorganic aluminum hypophosphite and application of inorganic aluminum hypophosphite in flame-retardant PBT |
CN114685856B (en) * | 2022-04-21 | 2024-02-20 | 兰州瑞朴科技有限公司 | Preparation method of diethyl aluminum phosphinate |
CN114806601B (en) * | 2022-05-10 | 2023-04-07 | 江苏利思德新材料有限公司 | Alkyl phosphinate composition and preparation method and application thereof |
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CN103788125A (en) * | 2013-12-31 | 2014-05-14 | 邓娟 | Additive for polymer and preparation method for additive |
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