CN105085988B - 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
- Publication number
- CN105085988B CN105085988B CN201510502916.1A CN201510502916A CN105085988B CN 105085988 B CN105085988 B CN 105085988B CN 201510502916 A CN201510502916 A CN 201510502916A CN 105085988 B CN105085988 B CN 105085988B
- Authority
- CN
- China
- Prior art keywords
- salt
- phosphinates
- polymer
- chloride
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5393—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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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% with formula（I）The dialkylphosphinic salts of shown structure；Component B：0.001wt% 0.5wt% chlorides, weight content of the chlorine element in total additive is 60 800ppm；Component C：0wt% 20wt% have formula（Ⅱ）The phostonic acid salt of shown structure；Component D：0wt% 0.9wt% have formula（Ⅲ）The phosphite of shown structure；It is 0wt% when component C, D is different, and the summation of A, B, C and D component is always 100wt%.Additive application of the invention is in polymer, flame-retardant polymer is greatly reduced to compounding combination unit Screw Corrosion degree, the energy frequently changed caused by screw rod in process is also reduced while reduction equipment processing cost to be lost with artificial, and causes that the polymeric articles whiteness obtained by extrusion molding is better than the modified polymeric articles of routine dialkylphosphinic salts.
Description
The application is Application No. 201410826125.X, and the applying date is 2014-12-26, and invention and created name is " 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 " point
Case application.
Technical field
The present invention relates to a kind of compositions of additives for polymer, and in particular to one kind contains chlorine element and alkyl
The dialkylphosphinic salts and its preparation method of phosphinate and/or phosphite and the flame-proofed thermoplastic polymerization being made from it
Thing moulding 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, the 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
Middle discovery is used, the flame-retardant polymer moulding compound of aluminum diethylphosphinate is added with process, to compounding combination dress
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
The complexing of property, nickel, chromium particularly to stainless steel clock etc. are with selectivity higher 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.
We have found to be mixed into part phostonic acid salt and/or a small amount of phosphonous acid in dialkylphosphinic salts by studying
Salt, can largely mitigate and be added with the flame-retardant polymer moulding compound of dialkylphosphinic salts in process
Corrosion to compounding combination unit screw rod, and on other performances of flame-retardant polymer almost without influence.Patent CN103154110 is public
Open and 1-80% phosphinates are mixed into dialkylphosphinic salts have played stabilizer, it has been found that because of the heat of aluminium phosphite
Decomposition temperature is relatively low, and during engineering plastics high temperature extrusion processing（Most of engineering plastics processing temperature is above 200
℃）Easily thermally decomposed, its decomposition can produce chance air spontaneously inflammable hypertoxic hydrogen phosphide other, we have discovered that its content is low
Corrosion resistance, stability and its security are more beneficial in 1%.
In addition, being used for dialkylphosphinic salts as fire retardant in flame-retardant polymer, flame-retardant polymer color can be made bright
Aobvious jaundice.And increasing substantially for polymer whiteness, it is always a big difficulty of industry, such as polyester this colorant, its
Product whiteness value L（Lab methods）When in the range of 80 ~ 95, whiteness value L differences 1 or so with the naked eye can be distinguished substantially, by the white of product
Angle value L (Lab methods) improves 1-2 point, also will be than larger technological break-through.Therefore, we pass through further investigation revealed that
The micro chloro thing in part and phostonic acid salt and/or a small amount of phosphite are mixed into simultaneously in dialkylphosphinic salts, no
Only can largely mitigate and be added with the flame-retardant polymer moulding compound of dialkylphosphinic salts in process
Corrosion to compounding combination unit screw rod, and cause to be added with the flame-retardant polymer moulding compound resistance of dialkylphosphinic salts
Combustion polymer color yellowing phenomenon can obtain extremely obvious improvement, and product whiteness is more preferably.
The content of the invention
In order to the whiteness of flame-retardant polymer for solving to be added with dialkylphosphinic salts and its moulding compound are processed
The problem of the corrosion of screw rod is combined the unit in journey to compounding, it is an object of the invention to provide one kind in dialkylphosphinic salts
Compositions of additives containing chlorine element and phostonic acid salt and/or phosphite structure and the fire-retardant thermoplastic being made from it
Property polymer in-mold moulding material.The additive application combines the unit Screw Corrosion journey to compounding in process in polymer
Degree is small, small to the ambient polymer extent of damage, and obtained flame-retardant polymer molding compositions product whiteness is more preferable, and to fire-retardant polymerization
Other performances of thing are 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% with formula（I）The dialkylphosphinic salts of shown structure,
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；
Component B:0.001wt%-0.5wt% chlorides, weight content of the chlorine element in total additive is 60-800ppm；
Component C：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（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 formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R4 is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 1 to 4；
It is 0wt% when component C, D is 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, weight content of the chlorine element in total additive is 70-450ppm, and preferred weight content is 70-
200ppm。
The chloride is selected from chlorinated alkenes, sodium chloride, potassium chloride, aluminium chloride, chlorine, hydrochloric acid, sodium hypochlorite, chloride idol
One or more in connection agent, chlorine-containing flame retardant, chloride surfactant or PVC；
Described chloride can also be selected from 1- chloroethylethyls phosphinates, 1- chloroethyls phosphinates, 1,2- dichloros
Ethyl diethyldithiocarbamate phosphinates, 1,2- Dichloroethyls phosphinates, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates,
4- chlorobutyl ethylphosphinic acids salt, 4- chlorobutyl butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethyl time phosphine
One or more in hydrochlorate, chlorocyclohexyl cyclohexyl phosphinates, chlorocyclohexyl phosphinates, described salt is sodium
Salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
The polymer is PBT, nylon, PPE, TPE, TPU or epoxy resin, preferably PBT, nylon or PPE.
One of a kind of preparation method of compositions of additives for polymer of the present invention, as follows：
Method one：
a）Hypophosphorous acid or its salt and chlorinated alkenes are added in a solvent, it is anti-with alkene under initiator and reaction promoter effect
Should, obtaining containing the dialkyl phosphinic acid of chloride or its salting liquid, its solution can be prepared with metallic compound reactant aqueous solution
Obtain the dialkylphosphinic salts containing chloride；
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 is obtained final product；
Wherein, the hypophosphites is sodium hypophosphite or potassium hypophosphite；The phosphite is sodium phosphite or phosphorous acid
Potassium；
The metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe；
The chlorinated alkenes are in 1- vinyl chloride, 1,2- dichloroethylene, chlorallylene, 4- chlorobutylenes or chloro cyclohexene
One or more.
Or method two：
Dialkyl phosphinic acid or its salting liquid are reacted with metal compound solution, dialkyl hypophosphorous acid salt is obtained, then
After miscible with the aqueous solution of additive I, the dialkylphosphinic salts containing chloride are obtained, then it is molten with phostonic acid or its salt
Liquid and/or phosphorous acid or its salting liquid is miscible obtains final product；
Wherein, the additive I is NaCl, KCl, AlCl3, chlorine, hydrochloric acid, sodium hypochlorite, chloride coupling agent or chloride
One or more in surfactant；
Described additive I can also select 1- chloroethylethyls phosphinates, 1- chloroethyls phosphinates, the chloroethenes of 1,2- bis-
Base ethylphosphinic acid salt, 1,2- Dichloroethyls phosphinates, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates, 4-
Chlorobutyl ethylphosphinic acid salt, 4- chlorobutyl butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethylphosphinic acid
One or more in salt, chlorocyclohexyl cyclohexyl phosphinates, chlorocyclohexyl phosphinates, described salt is sodium salt,
Sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
The metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe.
The dialkylphosphinic salts are dialkyl phosphinic acid sodium or dialkyl phosphinic acid potassium；The phosphite is phosphorous
Sour sodium or potassium phosphite.
Or method three：
Dialkyl phosphinic acid or its salting liquid are reacted with metal compound solution, dialkyl hypophosphorous acid salt is obtained, then
It is miscible with phostonic acid or its salting liquid and/or phosphorous acid or its salting liquid, finally in product filter process or washing process
Or add additive II to obtain final product in drying course；
Wherein, the additive II is NaCl, KCl, AlCl3, chlorine-containing flame retardant, chloride coupling agent, chloride surface-active
One or more in agent or PVC.
Described additive II can also select 1- chloroethylethyls phosphinates, 1- chloroethyls phosphinates, 1,2- dichloros
Ethyl diethyldithiocarbamate phosphinates, 1,2- Dichloroethyls phosphinates, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates,
4- chlorobutyl ethylphosphinic acids salt, 4- chlorobutyl butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethyl time phosphine
One or more of hydrochlorate, 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：
The raw material for preparing dialkyl hypophosphorous acid salt containing chlorine element will be added in solvent, is made in initiator and reaction promoter
With lower and olefine reaction, obtain containing the dialkyl phosphinic acid of chloride or its salting liquid, its solution is water-soluble with metallic compound
Liquid reaction can prepare the dialkylphosphinic salts containing chloride, then again with phostonic acid or its salting liquid and/or
Phosphorous acid or its salting liquid are miscible, obtain final product.
Wherein, the solvent is water；The initiator is azo-initiator, organic peroxide evocating agent or inorganic mistake
Peroxide initiator；The alkene is one or two the mixture in ethene and/or butylene；Described reaction promoter is boron
Sodium hydride or potassium borohydride.
The invention discloses a kind of above-mentioned compositions of additives for polymer 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 weight portions, the polymer of 50-70 weight portions or its mixture；Wherein, for polymer
Additive include：
Component A：80wt%-99.99wt% with formula（I）The dialkylphosphinic salts of shown structure,
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；
Component B:0.001wt%-0.5wt% chlorides, weight content of the chlorine element in total additive is 60-800ppm；
Component C：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（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 formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R4 is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 1 to 4；
It is 0wt% when component C, D is 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, weight content of the chlorine element in total additive is 70-450ppm, and preferred weight content is 70-
200ppm。
The chloride is selected from chlorinated alkenes, sodium chloride, potassium chloride, aluminium chloride, chlorine, hydrochloric acid, sodium hypochlorite, chloride idol
One or more in connection agent, chlorine-containing flame retardant, chloride surfactant or PVC；
Described chloride can also be selected from 1- chloroethylethyls phosphinates, 1- chloroethyls phosphinates, 1,2- dichloros
Ethyl diethyldithiocarbamate phosphinates, 1,2- Dichloroethyls phosphinates, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates,
4- chlorobutyl ethylphosphinic acids salt, 4- chlorobutyl butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethyl time phosphine
One or more in hydrochlorate, chlorocyclohexyl cyclohexyl phosphinates, chlorocyclohexyl phosphinates, described salt is sodium
Salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite.
The polymer is that the polymer is PBT, nylon, PPE, TPE, TPU or epoxy resin, preferably PBT, nylon or
PPE。
Flame-proofed thermoplastic polymer in-mold moulding material of the present invention, glass fibre and 1-5 also including 15-30 weight portions
Other auxiliary agents of weight portion.
The present invention compared with prior art, has the advantages that：
1）The dialkyl group containing chlorine element and phostonic acid salt and/or phosphite structure that the present invention is prepared
Phosphinates, used as the additive of flame-retardant polymer, the additive application in process, greatly drops in polymer
As the flame-retardant polymer of additive to compounding combination unit Screw Corrosion degree, reduction equipment adds low dialkylphosphinic salts
The energy frequently changed caused by screw rod in process is also reduced while work cost to be lost with artificial, and is caused by crowded
The polymeric articles whiteness that modeling is obtained is better than the modified polymeric articles of conventional dialkylphosphinic salts, and the plastics have been widened significantly
Additive range of application in the market；
2）Additive preparation process is simple, the safety, low production cost, extremely with practicality.
The present invention is further illustrated below by specific 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 636.0g（6mol）One hydration sodium hypophosphite, 5.5g（0.3%mol hypophosphorous acid ions）1,1- di-t-butyl peroxides
Change during -3,3,5- trimethyl-cyclohexanes, 1.8g sodium borohydrides and 900g water add autoclave, evacuate, with nitrogen displacement 3 times, take out
Sky, then simultaneously control pressure is 2.0MPa to be filled with ethene by pressure reducer, is heated to 95 DEG C of constant temperature 5h, is warming up to 100 DEG C, then in 5h
Continuously add 10.9g（0.6%mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, are warming up to
100 DEG C, 1h is incubated, cooling emptying obtains diethyl phosphinic acids sodium water solution 1902.7g, is equivalent to ethylene absorption amount
348.5g（The 103.7% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 98.3%
Ethyl phosphonous acid mol contents： 0%
Phosphorous acid mol contents： 0%
Other mol contents： 1.9%
Its aqueous solution 951.4g 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, 130 DEG C of drying of the filter cake for obtaining obtain aluminum diethylphosphinate to constant weight：375.4g, yield：
96.26%。
Embodiment 2：The preparation of one-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-cyclohexanes and 3.0g sodium borohydrides, evacuate, and with nitrogen displacement 5 times, evacuate, 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
1490.8g, is 289.2g equivalent to ethylene absorption amount（The 103.3% of theoretical amount）.
31P-NMR is analyzed：
Ethyl phosphonous acid mol contents： 98.2%
Phosphorous acid mol contents： 0%
Other mol contents： 1.8%
Its solution 223.6g 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, 130 DEG C of drying of the filter cake for obtaining obtain ethyl phosphonous acid aluminium to constant weight：174.8g, yield：
92.5%。
Embodiment 3：The preparation of one-component D aluminium phosphites
By 1110.0g, 1080g, 20wt% are instilled in 20wt% (0.33mol) aluminum sulfate aqueous solutions 1h（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
90.8g, yield：92.7%.
Embodiment 4-8：The preparation of component A+ components B
By 2120.0g（20mol）Sodium hypophosphite, 1320.0g（10mol）50% phosphinic acids, 27.2g（0.3%mol hypophosphorous acid
Ion）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes and 3000g water, add in autoclave, evacuate, and use nitrogen
Displacement 3 times, evacuates, and is quantitatively filled with chloroalkene, then simultaneously control pressure is 1.8MPa to be filled with ethene by pressure reducer, is heated to 87
DEG C, constant temperature 5h is heated to 95 DEG C, then continuously add 54.4g in 5h（0.6%mol hypophosphorous acid ions）1,1- di-t-butyl peroxides
Change -3,3,5- trimethyl-cyclohexanes, be warming up to 100 DEG C, be incubated 1h, cooling emptying obtains diethyl phosphinic acids sodium and diethyl
Phosphinic acids mixed solution 8297.8g, is 1772.1g equivalent to ethylene absorption amount（The 105.5% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 96.8%
Ethyl-butyl phosphinic acids mol contents： 2.1%
Ethylphosphinic acid mol contents： 1.2
Other mol contents： 0.9%
Diethyl phosphinic acids sodium and diethyl phosphinic acids mixed solution 829.7g are taken, 1600g water is added, 30% hydroxide is used
Sodium solution is neutralized to neutrality, is heated to 90 DEG C, is added dropwise by 333.0g in 1.5h（0.5mol）Patent alum and 1332g
The 20% Patent alum solution that water is configured to, 90 DEG C of insulation 1h, filtering, and with 2000L water washings 3 times, the filter cake for obtaining
130 DEG C of drying obtain aluminum diethylphosphinate to constant weight：373.2g, yield：95.7%.
According to above-mentioned steps, chloroalkene respectively from vinyl chloride, 1,2-dichloroethene, chlorallylene, 4- chlorobutylenes or
Chloro cyclohexene is substituted, and can prepare component A+B, wherein different according to its alkene, component B can be respectively:1- chloroethyl second
Base phosphinates, 1- chloroethyls phosphinates, 1,2- Dichloroethyl ethylphosphinic acids salt, 1,2- Dichloroethyls phosphinates, 3-
Chloropropyl propylphosphinic acid salt, 3- chloropropyls phosphinates, 4- chlorobutyl ethylphosphinic acids salt, 4- chlorobutyl butyl phosphinic acids
Salt, 4- chlorobutyls phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinates, chloro hexamethylene
Base phosphinates etc. so that contain micro chlorine element in aluminum diethylphosphinate.Its component is as shown in the table：
The mixture of 1. embodiment of table 4 ~ 8 is constituted
Embodiment 9 ~ 13：The preparation of component A+ components B
Aluminum diethylphosphinate is prepared with embodiment 1, is mixed with the chlorine-containing compound shown in table 2, prepare group
Divide A+ component B mixtures.
The mixture of 2. embodiment of table 9 ~ 13 is constituted
Embodiment 14：The preparation of component A+ components B
By 636.0g（6mol）One hydration sodium hypophosphite（Content of Cl element is 960ppm）、5.5g（0.3%mol hypophosphorous acid from
Son）1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes, 1.8g sodium borohydrides and 900g water are added in autoclave, are taken out
Sky, with nitrogen displacement 3 times, evacuates, then is filled with ethene by pressure reducer and control pressure is 2.0MPa, is heated to 95 DEG C of constant temperature
5h, is warming up to 100 DEG C, then continuously add 10.9g in 5h（0.6%mol hypophosphorous acid ions）1,1- di-tert-butyl peroxide -3,3,
5- trimethyl-cyclohexanes, are warming up to 100 DEG C, are incubated 1h, and cooling emptying obtains diethyl phosphinic acids sodium water solution 1904.6g, phase
When in ethylene absorption amount be 350.4g（The 104.3% of theoretical amount）.
31P-NMR is analyzed：
Diethyl phosphinic acids mol contents： 98.0%
Ethyl phosphonous acid mol contents： 0%
Phosphorous acid mol contents： 0%
Other mol contents： 2.0%
Its aqueous solution 952.3g 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, 130 DEG C of drying of the filter cake for obtaining obtain aluminum diethylphosphinate to constant weight：372.5g, yield：
95.5%。
Chlorinity：76ppm
Embodiment 15 ~ 25：The preparation of composition
The A+B mixtures of embodiment 4 ~ 14 are well mixed with the component C of embodiment 2 and/or the component D of embodiment 3, be can obtain
Fire retardant combination, its component is as shown in table 3.
Table 3. is used for the composition of the compositions of additives of polymer
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 aluminium phosphites, stir, filtering, are filtered twice with 600ml water washings, then washed with 0.2wt% aluminum chloride aqueous solutions 600ml
Wash, filter, be dried to obtain fire retardant combination.
Wherein, ethyl phosphonous acid aluminium content is 0.98wt%, and aluminium 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）Well mixed mixing, can obtain composition, and its component is as shown in continued 3：
The composition of continued 3. is constituted
Embodiment 27-38 and comparative example 4-9：The preparation of flame-proofed thermoplastic polymer in-mold moulding material
By the polymeric additive composition obtained by embodiment 15-26,4,6 and comparative example 1-3 230-260 DEG C with PBT,
Glass, auxiliary agent are by weight 10:50:30:(comparative example 4 is the blank sample contrast without compositions of additives, i.e., for 10 mixing
Weight ratio is 0:50:30:10 mixing), extruded from Bitruder, flame-proofed thermoplastic polymer in-mold moulding material, system is obtained
Sample tests its combustibility and mechanical property, measures result referring to table 4 below：
Flame-retardant PBT material property parameter table obtained in the addition polymeric additive composition of table 4
Continued 4：
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）, after calculating 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）On 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 show corresponding
Lab values.
For this colorant of PBT, L values are bigger, and color is whiter, are more easy to color matching.
7th, the examination criteria of chlorinity：PrEN 14582-2002 halogen detection methods.
Claims (18)
1. a kind of compositions of additives for polymer, including：
Component A：80wt%-99.99wt% with formula（I）The dialkylphosphinic salts of shown structure,
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；
Component B:0.001wt%-0.5wt% chlorides, weight content of the chlorine element in total additive is 60-800ppm；
Component C：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（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：0.4wt%-0.9wt% has formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R4 is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 1 to 4；
Component C is that 0 wt%, component D are not 0wt%, and the summation of A, B, C and D component is always 100wt%.
2. a kind of compositions of additives for polymer as claimed in claim 1, it is characterised in that R1, R2 are expressed as second
Base, propyl group and/or butyl.
3. a kind of compositions of additives for polymer as claimed in claim 1, it is characterised in that the chlorine element is total
Weight content in additive is 70-450ppm.
4. a kind of compositions of additives for polymer as claimed in claim 3, it is characterised in that the chlorine element is total
Weight content in additive is 70-200ppm.
5. a kind of compositions of additives for polymer as claimed in claim 1, it is characterised in that the chloride is selected from
Chlorinated alkenes, sodium chloride, potassium chloride, aluminium chloride, chlorine, hydrochloric acid, sodium hypochlorite, chloride coupling agent, chlorine-containing flame retardant, chloride table
Face activating agent, PVC, 1- chloroethylethyl phosphinates, 1- chloroethyls phosphinates, 1,2- Dichloroethyl ethylphosphinic acids salt,
1,2- Dichloroethyls phosphinates, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates, 4- chlorobutyl ethylphosphinic acids
Salt, 4- chlorobutyl butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl ring
One or more in ethylhexyl hypophosphorous acid salt, chlorocyclohexyl phosphinates.
6. 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.
7. a kind of compositions of additives for polymer as claimed in claim 6, it is characterised in that the polymer is
PBT, nylon or PPE.
8. 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 and chlorinated alkenes are added in a solvent, with olefine reaction under initiator and reaction promoter effect,
Obtain containing the dialkyl phosphinic acid of chloride or its salting liquid, its solution can be prepared with metallic compound reactant aqueous solution
Dialkylphosphinic salts containing chloride；
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 is obtained final product；
Wherein, the hypophosphites is sodium hypophosphite or potassium hypophosphite；The phosphite is sodium phosphite or potassium phosphite；
The metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe；
The chlorinated alkenes are the one kind in 1- vinyl chloride, 1,2- dichloroethylene, chlorallylene, 4- chlorobutylenes or chloro cyclohexene
Or it is several；
Or method two：
Dialkyl phosphinic acid or its salting liquid are reacted with metal compound solution, dialkyl hypophosphorous acid salt is obtained, then with add
Plus thing I the aqueous solution it is miscible after, obtain the dialkylphosphinic salts containing chloride, then with phostonic acid or its salting liquid
And/or phosphorous acid or its salting liquid is miscible obtains final product；
Wherein, the additive I is NaCl, KCl, AlCl3, chlorine, hydrochloric acid, sodium hypochlorite, chloride coupling agent or chloride surface live
Property agent, 1- chloroethylethyls phosphinates, 1- chloroethyls phosphinates, 1,2- Dichloroethyl ethylphosphinic acids salt, 1,2- dichloros
Ethylphosphinic acid salt, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates, 4- chlorobutyl ethylphosphinic acids salt, 4- chlorine
Butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl time phosphine
One or more in hydrochlorate, chlorocyclohexyl phosphinates；
Described salt is sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt, barium salt, zinc salt, molysite；
The metallic compound is the metallic compound of Mg, Ca, Al, Zn, Fe；
The dialkylphosphinic salts are dialkyl phosphinic acid sodium or dialkyl phosphinic acid potassium；The phosphite is sodium phosphite
Or potassium phosphite；
Or method three：
Dialkyl phosphinic acid or its salting liquid are reacted with metal compound solution, dialkyl hypophosphorous acid salt is obtained, then with alkane
Base phosphonous acid or its salting liquid and/or phosphorous acid or its salting liquid are miscible, finally in product filter process or washing process or baking
Additive II is added to obtain final product during dry；
Wherein, the additive II is NaCl, KCl, AlCl3, chlorine-containing flame retardant, chloride coupling agent, chloride surfactant,
PVC, 1- chloroethylethyl phosphinates, 1- chloroethyls phosphinates, 1,2- Dichloroethyl ethylphosphinic acids salt, the chloroethenes of 1,2- bis-
Base phosphinates, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates, 4- chlorobutyl ethylphosphinic acids salt, 4- neoprenes
Base butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl cyclohexyl phosphinic acids
One or more in salt, 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 for preparing dialkyl hypophosphorous acid salt containing chlorine element is added in a solvent, under initiator and reaction promoter effect
With olefine reaction, obtain containing the dialkyl phosphinic acid of chloride or its salting liquid, its solution is anti-with the metallic compound aqueous solution
The dialkylphosphinic salts containing chloride should be prepared, then again with phostonic acid or its salting liquid and/or phosphorous
Acid or its salting liquid are miscible, obtain final product.
9. the preparation method of a kind of compositions of additives for polymer as claimed in claim 8, 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 one or two the mixture in ethene and/or butylene；Described reaction promoter is sodium borohydride or potassium borohydride.
10. a kind of compositions of additives for polymer as claimed in claim 1 as fire retardant purposes.
A kind of 11. flame-proofed thermoplastic polymer in-mold moulding materials comprising compositions of additives as claimed in claim 1, including 5-20
The additive for polymer of weight portion, the polymer of 50-70 weight portions or its mixture；Wherein, adding for polymer
Plus agent includes：
Component A：80wt%-99.99wt% with formula（I）The dialkylphosphinic salts of shown structure,
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；
Component B:0.001wt%-0.5wt% chlorides, weight content of the chlorine element in total additive is 60-800ppm；
Component C：0wt%-20wt% has formula（Ⅱ）The phostonic acid salt of shown structure,
（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：0.4wt%-0.9wt% has formula（Ⅲ）The phosphite of shown structure；
（Ⅲ）
Wherein, R4 is expressed as H；M is Mg, Ca, Al, Zn, Fe；M is 1 to 4；
Component C is that 0wt%, component D are not 0wt%, and the summation of A, B, C and D component is always 100wt%.
12. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 11, it is characterised in that R1, R2 be expressed as ethyl,
Propyl group and/or butyl.
13. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 11, it is characterised in that the chlorine element adds always
Plus the weight content in agent is 70-450ppm.
14. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 13, it is characterised in that the chlorine element adds always
Plus the weight content in agent is 70-200ppm.
15. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 11, it is characterised in that the chloride is selected from chlorine
Change alkene, sodium chloride, potassium chloride, aluminium chloride, chlorine, hydrochloric acid, sodium hypochlorite, chloride coupling agent, chlorine-containing flame retardant, chloride surface
Activating agent, PVC, 1- chloroethylethyl phosphinates, 1- chloroethyls phosphinates, 1,2- Dichloroethyl ethylphosphinic acids salt, 1,
2- Dichloroethyls phosphinates, 3- chloropropyl propylphosphinic acids salt, 3- chloropropyls phosphinates, 4- chlorobutyl ethylphosphinic acids
Salt, 4- chlorobutyl butyl phosphinates, 4- chlorobutyls phosphinates, chlorocyclohexyl ethylphosphinic acid salt, chlorocyclohexyl ring
One or more in ethylhexyl hypophosphorous acid salt, chlorocyclohexyl phosphinates.
16. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 11, it is characterised in that the polymer be PBT,
Nylon, PPE, TPE, TPU or epoxy resin.
17. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 16, it is characterised in that the polymer be PBT,
Nylon or PPE.
18. flame-proofed thermoplastic polymer in-mold moulding materials as claimed in claim 11, it is characterised in that also including 15-30 weight
The glass fibre of part and other auxiliary agents of 1-5 weight portions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510502916.1A CN105085988B (en) | 2014-12-26 | 2014-12-26 | A kind of compositions of additives and its preparation method for polymer and the flame-proofed thermoplastic polymer in-mold moulding material being made from it |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510502916.1A CN105085988B (en) | 2014-12-26 | 2014-12-26 | 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 |
| CN201410826125.XA CN104497504B (en) | 2014-12-26 | 2014-12-26 | A kind of compositions of additives for polymkeric substance and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410826125.XA Division CN104497504B (en) | 2014-12-26 | 2014-12-26 | A kind of compositions of additives for polymkeric substance and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105085988A CN105085988A (en) | 2015-11-25 |
| CN105085988B true CN105085988B (en) | 2017-06-30 |
Family
ID=52938967
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510502916.1A Active CN105085988B (en) | 2014-12-26 | 2014-12-26 | 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 |
| CN201410826125.XA Expired - Fee Related CN104497504B (en) | 2014-12-26 | 2014-12-26 | A kind of compositions of additives for polymkeric substance and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410826125.XA Expired - Fee Related CN104497504B (en) | 2014-12-26 | 2014-12-26 | A kind of compositions of additives for polymkeric substance and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN105085988B (en) |
| WO (1) | WO2016101800A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105085988B (en) * | 2014-12-26 | 2017-06-30 | 肖群 | 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 |
| 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 |
| DE102017212100A1 (en) * | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additive mixtures for plastics, laser-markable polymer compositions containing them and their use |
| 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 |
| CN111825883A (en) * | 2019-04-15 | 2020-10-27 | 黎杰 | Metal complex salts of polydialkylphosphinic acids and/or mixtures thereof, and use 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788125A (en) * | 2013-12-31 | 2014-05-14 | 邓娟 | Additive for polymer and preparation method for additive |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19708726A1 (en) * | 1997-03-04 | 1998-09-10 | Hoechst Ag | Flame-retardant polymer molding compounds |
| DE10359815A1 (en) * | 2003-12-19 | 2005-07-28 | Clariant Gmbh | Process for the preparation of dialkylphosphinic salts |
| JP5548625B2 (en) * | 2008-03-03 | 2014-07-16 | クラリアント・ファイナンス・（ビーブイアイ）・リミテッド | Process for producing polyamide and polyester molding materials with flame resistance, non-corrosion and good flow |
| DE102010048025A1 (en) * | 2010-10-09 | 2012-04-12 | Clariant International Ltd. | Flame retardant stabilizer combination for thermoplastic polymers |
| 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 |
| DE102013004046A1 (en) * | 2013-03-08 | 2014-09-11 | Clariant International Ltd. | Flame retardant polyamide composition |
| CN105085988B (en) * | 2014-12-26 | 2017-06-30 | 肖群 | 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 |
-
2014
- 2014-12-26 CN CN201510502916.1A patent/CN105085988B/en active Active
- 2014-12-26 CN CN201410826125.XA patent/CN104497504B/en not_active Expired - Fee Related
-
2015
- 2015-12-12 WO PCT/CN2015/097211 patent/WO2016101800A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788125A (en) * | 2013-12-31 | 2014-05-14 | 邓娟 | Additive for polymer and preparation method for additive |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016101800A1 (en) | 2016-06-30 |
| CN105085988A (en) | 2015-11-25 |
| CN104497504B (en) | 2016-03-30 |
| CN104497504A (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105085988B (en) | 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 | |
| CN104371142B (en) | A kind of compositions of additives for polymer and its preparation method and consisting of flame-proofed thermoplastic polymer in-mold moulding material | |
| CN103788125B (en) | Additive for polymer and preparation method for additive | |
| ES2532548T3 (en) | Process for the preparation of alkyl phosphonic acids and their esters and salts, by oxidation of alkyl phosphonous acids, and their use | |
| EP1832595B1 (en) | Compounds of mono-carboxyl functionalised dialkylphosphine acid salts and other components, a method for their manufacture and their application | |
| ES2433221T3 (en) | Process for the preparation of dialkyl phosphonic acids mono-functionalized with hydroxy or their esters and salts, by vinyl esters of a carboxylic acid, and their use | |
| EP2379573B1 (en) | Process for preparing ethylenedialkylphosphinic acids, esters and salts by means of acetylene and use thereof | |
| EP2352740B1 (en) | Method for producing dialkylphosphinic acids and esters and salts thereof by means of acrylic acid derivatives and use thereof | |
| CN107189098A (en) | A kind of additive and its preparation method for polymer and application and the flame-retardant polymer moulding compound being made from it | |
| ES2525547T3 (en) | Process for the preparation of dialkyl phosphonic acids mono-functionalized with amino or its esters and salts by means of acrylonitriles and their use | |
| ES2445096T3 (en) | Process for the preparation of monohydroxy functionalized dialkylphosphinic acids, esters and salts by allyl alcohols and their use | |
| ES2448579T3 (en) | Process for the preparation of dialkyl phosphonic acids mono-functionalized with carboxy and their esters and salts by alkylene oxides and their use | |
| ES2448577T3 (en) | Process for the preparation of dialkyl phosphonic acids mono-functionalized with carboxy and their esters and salts by means of vinyl esters of a carboxylic acid and their use | |
| CN105646938B (en) | 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 | |
| CN103102367B (en) | Preparation method and application of dialkyl phosphinate with high density and large diameter | |
| DE102008056342A1 (en) | Process for the preparation of dialkylphosphinic acids, esters and salts by means of acrylonitriles and their use | |
| US20070029532A1 (en) | Flame retardant preparation | |
| DE102008056227A1 (en) | Process for the preparation of dialkylphosphinic acids, esters and salts by means of vinyl compounds and their use | |
| CN103172668A (en) | Monoalkyl/dialkyl phosphinate and preparation method thereof | |
| CN107207780A (en) | Flame-retardant mixture and its preparation | |
| KR101453836B1 (en) | Hypophosphorous Type Flame Retardants and Manufacturing Method Thereof | |
| CN104072537B (en) | High-purity diethyl phosphinates and its preparation process | |
| EP3197905B1 (en) | Method for producing ethylenedialkylphosphinic acids, esters and salts, and the use thereof as flame retardants | |
| CN113929967A (en) | Phosphorus-nitrogen double salt and preparation method thereof, flame retardant and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |