CN104379669A - Flame-proof polyester comprising polyacrylonitrile homopolymerisates - Google Patents
Flame-proof polyester comprising polyacrylonitrile homopolymerisates Download PDFInfo
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- CN104379669A CN104379669A CN201380032222.5A CN201380032222A CN104379669A CN 104379669 A CN104379669 A CN 104379669A CN 201380032222 A CN201380032222 A CN 201380032222A CN 104379669 A CN104379669 A CN 104379669A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K3/02—Elements
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to thermoplastic moulding materials containing A) 10 to 97 wt.% of a thermoplastic polyester, B) 0.1 to 60 wt.% of red phosphorus, C) 1 to 25 wt.% of a polyacrylonitrile homopolymerisate, D) 0 to 50 wt.% of a fibre or particle-shaped filler, and E) 0 to 60 wt.% of further additives, the sum of the weight percentages A) to E) equalling 100%.
Description
The present invention relates to thermoplastic composition, comprise
A) thermoplastic polyester of 10 to 97 % by weight,
B) red phosphorus of 0.1 to 60 % by weight,
C) polyacrylonitrile homopolymer of 1 to 25 % by weight,
D) 0 to 50 % by weight threadiness or particulate fillers, and
E) other additives of 0 to 60 % by weight,
Wherein A) to E) total weight percent be 100%.
The invention further relates to the purposes of this type of moulding compound for the production of fiber, paper tinsel and moulded product, and the moulded product of any type of gained, fiber and paper tinsel.
Known being joined by red phosphorus in thermoplastics (especially strengthen or fill polyester) can cause effective flame retardant resistance (such as JP-A-2001/226570, JP-A-2000/328065).Such as, but when red phosphorus is exposed in unfavourable condition (such as, high temperature, humidity or there is alkali or oxygen), it tends to form degradation production, and phosphuret-(t)ed hydrogen and monovalence are to the phosphoric acid of pentavalent.
Stabilization can be reached by the oxide compound or oxyhydroxide that add zinc, magnesium or copper.In DE-A-2625691, except obtain described stability by metal oxide except, phosphorus particle can become complicated, and the stabilization of system is often unsatisfactory in addition.
JP-A-2005/126633 discloses the polyolefine comprising the polyacrylonitrile be combined with red phosphorus and metal hydroxides.
The performance that the needs of known moulding compound improve is smoke density and heat release rate.The residual quantity increased after burning is also desirable, because gained carbon-coating can hinder the development of fire, thus reduces total Heat liberation unit and total amount of being fuming.
Therefore, the object of the invention is to develop thermoplastic polyester moulding masses, it comprises the red phosphorus as fire retardant and presents smoke density and the heat release rate of reduction, and the residual quantity after the burning increased.
Moulding compound of the present invention comprises 10 to 97 % by weight, and preferably 20 to 95 % by weight, particularly at least one thermoplastic polyester of 20 to 80 % by weight is as component (A).
Normally used polyester A) be those compounds based on aromatic dicarboxylic acid, aliphatic series or aromatic dihydroxy compound.
First group of preferred polyester is polyalkylene terephthalates (polyalkyleneterephthalate), and particularly those have the polyalkylene terephthalates of 2 to 10 carbon atoms at alcohol moiety.
This type of polyalkylene terephthalates is that itself is known and be described in document.Their main chain comprises the aromatic ring derived from aromatic dicarboxylic acid.Also substituting group can be there is in aromatic ring, such as halogen, such as chlorine or bromine; Or C
1to C
4alkyl, such as methyl, ethyl, sec.-propyl or n-propyl or normal-butyl, isobutyl-or the tertiary butyl.
These polyalkylene terephthalates are by carrying out in a manner known per se reacting with aliphatic dihydroxy compound by aromatic dicarboxylic acid or its ester or other ester formative derivatives (ester-forming derivative) and obtain.
Preferred dicarboxylic acid is 2,6-naphthalene dicarboxylic acids (2,6-naphthalenedicarboxylic acid), terephthalic acid, m-phthalic acid, and their mixture.Nearly 30mol%, preferably the aromatic dicarboxylic acid of 10mol% can be replaced by aliphatic series or alicyclic dicarboxylic acid's (such as, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid and cyclohexane dicarboxylic acid) at the most.
Preferred aliphatic dihydroxy compound is the glycol with 2 to 6 carbon atoms, especially 1,2-ethylene glycol, 1, ammediol, BDO, 1,6-hexylene glycol, 1,4-hexylene glycol, 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol and neopentyl glycol (neopentyl glycol), and their mixture.
Particularly preferred polyester (A) is the polyalkylene terephthalates derived from the alkanediol with 2 to 6 carbon atoms.In these compounds, particularly preferably polyethylene terephthalate (polyethylene terephthalate), Poly(Trimethylene Terephthalate) (polypropylene terephthalate) and polybutylene terephthalate (polybutyleneterephthalate), and their mixture.Further preferably PET and/or PBT, wherein these compounds comprise nearly 1 % by weight, preferably nearly 0.75 % by weight 1,6-hexylene glycol and/or 2-methyl isophthalic acid, 5 pentanediols are as other monomeric units.
According to ISO 1628, the limiting viscosity (intrinsic viscosity) of polyester (A) is usually 50 to 220, preferably 80 to 160 scope in (at 25 DEG C of temperature, measuring in phenol/orthodichlorobenzene mixture (weight ratio of the 1:1) solution of 50 % by weight intensity).
Particularly preferably polyester, its content of carboxyl end group is nearly 100 milligramequivalent every kilogram of polyester, preferably nearly 50 milligramequivalent every kilogram of polyester, and particularly 40 milligramequivalent every kilogram of polyester at the most.This kind polyester is prepared by the method in such as DE-A 44 01 055.Content of carboxyl end group is measured by volumetry (such as potentiometric titration) usually.
Especially, the mixture that preferred moulding compound comprises the polyester except PBT---such as polyethylene terephthalate (PET)---is as component A).Such as, the ratio of the polyethylene terephthalate in mixture is preferably and reaches 50 % by weight, is in particular 10 to 35 % by weight, the component A in 100 % by weight).
Also advantageously can use the PET regenerant (being also referred to as waste material PET) optionally mixed with polyalkylene terephthalates (as PBT).
Regenerant is generally
1) those of Post Industrialization regenerant are called as: it is the processing waste during polycondensation or treating processes, such as, from the slag of injection moulding, from injection moulding or the starting material extruded, or from the edge pruning material of extruded sheet or paper tinsel, or
2) regenerant after consumption: it is the plastic article being collected and processing after ultimate consumer uses.At quantitative aspects, the blow molding PET bottle for mineral water, soft drink and fruit juice is primary articles undoubtedly.
The regenerant of two types all can be used as earth material or use with granular form.In the latter case, thick regenerant, through abstraction and purification, then melts, and utilizes extrusion machine to carry out granulation.This is conducive to process and unrestricted flow usually, and for the treatment of the metering of other steps in process.
Regenerant used can be granular or for grinding again form.Edge length more than 10mm, preferably should not be less than 8mm.
Because polyester stands hydrolytic scission (moisture owing to trace) in treating processes, it is desirable for being undertaken predrying by regenerant.Dried residual moisture content is preferably < 0.2%, is in particular < 0.05%.
Another mentioned group polyester is the full-aromatic polyester derived from aromatic dicarboxylic acid and aromatic dihydroxy compound.
Suitable aromatic dicarboxylic acid is the aforesaid compound for polyalkylene terephthalates.The m-phthalic acid of mixture by 5 to 100mol% of preferred use and the terephthalic acid of 0 to 95mol%, the m-phthalic acid of especially about 50 to about 80mol% and 20 to about 50mol% terephthalic acid form.
Aromatic dihydroxy compound preferably has general formula
Wherein Z has the alkylidene group or ring alkylidene group, the arylidene with nearly 12 carbon atoms, carbonyl, alkylsulfonyl, Sauerstoffatom or sulphur atom or chemical bond that reach 8 carbon atoms, and m is 0 to 2.The phenylene of these compounds also can by C
1-C
6-alkyl or C
1-C
6-alkoxyl group and fluorine, chlorine or bromine replace.
Example for the parent compound of these compounds is
Dihydroxybiphenyl,
Two (hydroxy phenyl) alkane,
Two (hydroxy phenyl) naphthenic hydrocarbon,
Two (hydroxy phenyl) sulfide,
Two (hydroxy phenyl) ether,
Two (hydroxy phenyl) ketone,
Two (hydroxy phenyl) sulfoxide,
α, α '-two (hydroxy phenyl) dialkyl benzene,
Two (hydroxy phenyl) sulfone, two (hydroxy benzoyl) benzene,
Resorcinol and Resorcinol, and the cycloalkylation of these compounds and ring halide derivative.
In these compounds, preferably
4,4 '-dihydroxybiphenyl,
2,4-bis-(4 '-hydroxy phenyl)-2-methylbutane,
α, α '-two (4-hydroxy phenyl)-p-Diisopropylbenzene,
2,2-bis-(3 '-methyl-4 '-hydroxy phenyl) propane, and
2,2-bis-(3 '-chloro-4 '-hydroxy phenyl) propane,
And particularly preferably
2,2-bis-(4 '-hydroxy phenyl) propane,
2,2-bis-(3 ', 5-dichloro dihydroxy phenyl) propane,
1,1-bis-(4 '-hydroxy phenyl) hexanaphthene,
3,4 '-dihydroxy benaophenonel,
4,4 '-dihydroxy diphenylsulphone and
2,2-bis-(3 ', 5 '-dimethyl-4 '-hydroxy phenyl) propane
And their mixture.
Certainly, also polyalkylene terephthalates and full-aromatic polyester can be used.These compounds generally include the polyalkylene terephthalates of 20 to 98 % by weight and the full-aromatic polyester of 2 to 80 % by weight.
Certainly, also polyester block copolymer can be used, such as copolyether ester.This series products itself is known and be described in document, such as, in US-A 3 651 014.Corresponding product is also commercially available, such as,
(DuPont).
According to the present invention, term polyester also comprises halogen polycarbonate.The example of suitable halogen polycarbonate is those compounds based on the xenol of following general formula
Wherein Q is singly-bound, C
1-C
8-alkylidene group, C
2-C
3-alkylidene group, C
3-C
6-ring alkylidene group, C
6-C
12-arylidene or-O-,-S-or-SO
2-, and m is the integer of 0 to 2.
The phenylene group of xenol also can have substituting group, such as, C
1-C
6-alkyl or C
1-C
6-alkoxyl group.
The example of the molecular formula of preferred xenol is Resorcinol, Resorcinol, 4,4 '-dihydroxybiphenyl, 2, two (4-hydroxy phenyl) propane of 2-, 2,4-two (4-hydroxy phenyl)-2-methyl-butan and 1,1-bis(4-hydroxyphenyl) cyclohexanes.Two (4-hydroxy phenyl)-3,3, the 5-trimethyl-cyclohexanes of particularly preferably 2,2-two (4-hydroxy phenyl) propane and 1,1-bis(4-hydroxyphenyl) cyclohexanes, and 1,1-.
Homo-polycarbonate or Copolycarbonate are all suitable as component A), and the Copolycarbonate of preferred dihydroxyphenyl propane, and bisphenol A homo thing.
Suitable polycarbonate can carry out branching with currently known methods, even preferably by the compound of at least trifunctional being incorporated to 0.05 to 2.0mol% (total amount with the bis-phenol used), such as those compounds with more than three phenolic hydroxyl groups carry out branching.
The relative viscosity η of verified particularly suitable polycarbonate
relbe 1.10 to 1.50, be in particular 1.25 to 1.40.This corresponds to 10 000 to 200 000g/mol, preferably the average molar mass M of 20 000 to 80 000g/mol
w(weight average).
The xenol of general formula is own known or prepares by currently known methods.
Polycarbonate can such as be reacted with interfacial by xenol and phosgene and be prepared, or reacted by xenol and phosgene with homogeneous method (being called as pyridine method) and prepare, and molecular weight required in all cases obtains in a known way by using appropriate known chain terminator.(about the polycarbonate containing polydiorganosiloxane, see, such as DE-A 33 34 782.)
The example of suitable chain terminator be the alkylphenol of phenol, p-tert-butylphenol or long-chain (such as, 4-(1 in DE-A 28 42 005,3-tetramethyl butyl) phenol) or monoalkyl phenol or DE-A-35 06 472 in alkyl substituent on the total number of carbon atoms be the dialkyl phenol of 8 to 20, such as n nonylphenol, 3,5-di-tert-butylphenol, p-tert-octyl phenol, to 4-dodecylphenol, 2-(3,5-dimethyl heptyl) phenol and 4-(3,5-dimethyl heptyl) phenol.
For the purposes of the present invention, if halogen carbonic ether is by halogen bis-phenol, halogen chain terminator and the polycarbonate that forms of halogen branching agent that uses, wherein for the purposes of the present invention, it is halogen-containing that the content being in the hydrolyzable chlorine (such as, prepared with interfacial by polycarbonate and phosgene and obtain) of the minor amount of ppm level is not regarded as term.For the purposes of the present invention, the content of hydrolyzable chlorine is in this kind of polycarbonate of ppm level is halogen polycarbonate.
Other suitable component A that can mention) be amorphous polyester carbonic ether, wherein in preparation process, phosgene is substituted by aromatic dicarboxylic acid unit (such as, m-phthalic acid and/or terephthalic acid units).Details about this can see EP-A 711 810.
EP-A 365 916 describes other the suitable Copolycarbonates had as the group of naphthene base of monomeric unit.
Dihydroxyphenyl propane also can be substituted by bis-phenol TMC.This kind of polycarbonate can purchased from Bayer, and trade mark is
Fire retardant B of the present invention) be mainly red phosphorus, it is combined with the moulding compound of glass fibre-enhancing especially, and it can untreated form use.
But, specially suitable material is prepared product, wherein phosphorus surface scribbles low-molecular-weight liquid material, such as, silicone oil, paraffin oil, or the ester class of phthalic acid (is in particular dioctyl phthalate (DOP), see EP 176 836), or hexanodioic acid, or polymkeric substance or oligomeric compounds (such as resol or aminoplastics, or urethane (see EP-A 384 232, DE-A 196 48 503)).The amount be made up of these " deterrent (phlegmatizing agents) " is generally 0.05 to 5 % by weight, the B in 100 % by weight).
The other materials being suitable as fire retardant is the enriched material of red phosphorus such as in polymeric amide or elastomerics.Specially suitable concentrated polymer is polyolefin homopolymer and multipolymer.But the ratio of concentrated polymer amounts to and is no more than 35 % by weight, with component A in moulding compound of the present invention) and weighing scale B).
Preferred concentrate composition is
B
1) 30 to 90 % by weight, preferably 45 to 70 % by weight polymeric amide or elastomerics,
B
2) 10 to 70 % by weight, the preferably red phosphorus of 30 to 55 % by weight.
Polymeric amide for Masterbatch (masterbatch) is preferably PA6 and/or PA66, can not be had a negative impact to moulding compound by incompatible appearance or different melting points.
Be dispersed in the mean size (d of the phosphorus particle in moulding compound
50) preferably in the scope of 0.0001 to 0.5mm, particularly preferably in the scope of 0.001 to 0.2mm.
In moulding compound of the present invention, B component) content be 0.1 to 60 % by weight, be preferably 0.5 to 40 % by weight, be in particular 1 to 15 % by weight, in A) to E) whole components.
Moulding compound of the present invention comprises 1 to 25 % by weight, and preferably 1 to 15 % by weight, the polyacrylonitrile homopolymer of special 1 to 11 % by weight is as component C).This is the term of the polymkeric substance of following structure
This kind of homopolymer can be prepared by the Raolical polymerizable of vinyl cyanide and initiator, and industrial polymerisation process conventional herein betides in water usually.
The molecular-weight average M of preferred polyacrylonitrile
wbe 10 000 to 400 000, be in particular 50000 to 350 000, according to DIN 55672-2:2008-06, by means of GPC, part 2, PMMA is as elutriant (standard).
Particularly preferred polyacrylonitrile is with the form of powder, particle, sheet or block and other component A) and B) and optional D) and E) to mix, then compounding (compound).
The threadiness that can mention or particulate fillers D) (being different from E) is carbon fiber, glass fibre, granulated glass sphere, soft silica, Calucium Silicate powder, calcium metasilicate, magnesiumcarbonate, kaolin, chalk, flint, mica, barium sulfate and feldspar, and the usage quantity of these materials spendable is 1 to 50 % by weight, special 5 to 45 % by weight, preferably 10 to 40 % by weight.
The preferred fibrous filler that can mention is carbon fiber, aramid fiber (aramid fiber) and potassium titanate fiber, and particularly preferably with the glass fibre that E glass forms exists.These can be used as rove or commercially available staple glass form uses.
Fibrous filler useful silanes compound carries out surface preparation to improve the consistency with thermoplastics.
Suitable silane compound has following general formula:
(X-(CH
2)
n)
k-Si-(O-C
mH
2m+
1)
4-k
Wherein substituently to be defined as follows:
N is 2 to 10, preferably the integer of 3 to 4,
M is 1 to 5, preferably the integer of 1 to 2, and
K is the integer of 1 to 3, is preferably 1.
Preferred silane compound is aminopropyl trimethoxysilane (aminopropyltrimethoxysilane), ammonia butyl trimethoxy silane (aminobutyltrimethoxysilane), aminopropyl triethoxysilane (aminopropyltriethoxysilane), ammonia butyl triethoxyl silane (aminobutyltriethoxysilane), and comprises the silane of glycidyl of alternatively base X accordingly.
Amount for the silane compound of top coat is generally 0.01 to 2 % by weight, is preferably 0.025 to 1.0 % by weight, is in particular 0.05 to 0.5 % by weight (in D)).
Needle-like (acicular) mineral filler is also suitable.
For the purposes of the present invention, needle-like mineral filler is have the strong mineral filler stretching needle-like feature.Example is acicular wollastonite.The L/D (length: diameter) that mineral preferably have, than being 8:1 to 35:1, is preferably 8:1 to 11:1.Mineral filler can optionally utilize above-mentioned silane compound to carry out pre-treatment, but pre-treatment is dispensable.
Other weighting agents that can mention are kaolin, calcined kaolin, talcum and chalk, and other stratiform or acicular nanometer weighting agent, and the preferred consumption of these weighting agents is 0.1 to 10%.Preferred material for this object is boehmite (boehmite), wilkinite (bentonite), polynite (montmorillonite), vermiculite (vermiculite), hectorite (hectorite) and hectorite (laponite).According to prior art, in order to obtain the excellent compatibility of laminar nano weighting agent and organic binder bond, carry out organically-modified to laminar nano weighting agent.Stratiform or acicular nanometer weighting agent being joined in nano composite material of the present invention makes physical strength improve further.
Moulding compound of the present invention can comprise 0 to 60 % by weight, particularly nearly 50 % by weight, particularly nearly 30 % by weight other additives and processing aid as component E).
Moulding compound of the present invention can comprise 0 to 5 % by weight, preferably 0.05 to 3 % by weight, particularly 0.1 to 2 % by weight by having 10 to 40 carbon atoms, preferably 16 to 22 carbon atoms saturated or unsaturated aliphatic carboxylic acid with there are 2 to 40 carbon atoms, preferably at least one ester that forms of the saturated fatty alcohol of 2 to 6 carbon atoms or amine or acid amides are as component E).
Carboxylic acid can be unitary or di-carboxylic acid.The example that can mention is n-nonanoic acid (pelargonic acid) palmitinic acid (palmitic acid), lauric acid (lauric acid), margaric acid (margaricacid), dodecanedioic acid (dodecanedioic acid), docosoic acid (behenic acid), particularly preferably stearic acid (stearic acid), capric acid (capric acid), and montanic acid (montanic acid) (there is the mixture of the lipid acid of 30 to 40 carbon atoms).
Fatty alcohol can contain 1-to 4-hydroxyl.Suitable alcohol is propyl carbinol, n-Octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, tetramethylolmethane, preferred ethylene glycol, glycerol, tetramethylolmethane.
Aliphatic amide can be 1-to 3-valency.The example of these aliphatic amides is stearylamine (stearylamine), quadrol, propylene diamine, hexanediamine, two (6-ammonia hexyl) amine, particularly preferably quadrol and hexanediamine.Ester class and amides are preferably distearin (glycerol distearate), Tristearoylglycerol (glycerol tristearate), quadrol SUNSOFT Q-182S (ethylenediaminedistearate), monopalmitin (glycerol monopalmitate), trilaurin (glycerol trilaurate), single Glyceryl Behenate (glycerol monobehenate), with pentaerythritol tetrastearate (pentaerythritol tetrastearate).
Also can use the mixture that the various ester of any required blending ratio or various acid amides or ester are combined with acid amides.
Other conventional additives E) such as reaching 40 % by weight, preferably reach the elastomeric polymer (usually also referred to as anti-impact modifier, elastomerics, rubber) of 30 % by weight.
These additives E) be generally the multipolymer be preferably made up of at least two kinds in following monomer: ethene, propylene, divinyl, iso-butylene, isoprene, chloroprene, vinyl-acetic ester, vinylbenzene, vinyl cyanide, and acrylate and/or the methacrylic ester in alkoxide component with 1 to 18 carbon atom.
This base polymer is such as described in Houben-Weyl, Methoden der organischenChemie, 14/1st volume (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), 392-406 page, and the monograph write by C.B.Bucknall " Toughened Plastics " (Applied Science Publishers, London, UK, 1977) in.
These type of more elastomeric preferred types are described below.
This type of elastomeric preferred type is called as the elastomerics of second third (EPM) rubber and Ethylene Propylene Terpolymer (EPDM) rubber for those.
EPM rubber is usually almost without residual double bonds, but every 100 carbon atoms of EPDM rubber can have 1 to 20 double bond.
The example of the diene monomers for EPDM rubber that can mention is conjugated diolefine, such as isoprene and divinyl; There is the non-conjugated diene of 5 to 25 carbon atoms, such as Isosorbide-5-Nitrae-pentadiene, Isosorbide-5-Nitrae-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5 hexadienes and Isosorbide-5-Nitrae-octadiene; Cyclic diolefine, such as cyclopentadiene, cyclohexadiene, cyclooctadiene and Dicyclopentadiene (DCPD); And alkenyl norbornene, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornylene, 2-methylallyl-5-norbornylene and 2-pseudoallyl-5-norbornylene; And three cyclic diolefine, such as 3-methyl three ring [5.2.1.0
2,6]-3,8-decadiene, and their mixture.Preferably 1,5-hexadiene, 5-ethylidene norbornene and Dicyclopentadiene (DCPD).The diene content of EPDM rubber is preferably 0.5 to 50 % by weight, is in particular 1 to 8 % by weight, with the total weight of rubber.
EPM and EPDM rubber also can preferably grafting active carboxylic acid or their derivative.Be vinylformic acid, methacrylic acid and derivative thereof at the example of these these compounds that can mention, such as, (methyl) glycidyl acrylate, and maleic anhydride.
The multipolymer of the ester of ethene and vinylformic acid and/or methacrylic acid and/or these acid organizes preferred rubber for another.In addition, described rubber also can comprise dicarboxylic acid, such as toxilic acid and fumaric acid; Or the derivative of these dicarboxylic acid, such as ester and acid anhydrides; And/or comprise the monomer of epoxide group.These monomers comprising dicarboxylic acid derivatives or comprise epoxide group comprise dicarboxylic acid group and/or epoxide group and the monomer that general formula is I, II, III or IV is included into in rubber preferably by adding in monomer mixture.
R
1C(COOR
2)＝C(COOR
3)R
4(I)
Wherein R
1to R
9for hydrogen or the alkyl with 1 to 6 carbon atom, and m is the integer of 0 to 20, and g is the integer of 0 to 10, and p is the integer of 0 to 5.
R
1to R
9be preferably hydrogen, wherein m is 0 or 1, and g is 1.Corresponding compound is toxilic acid, fumaric acid, maleic anhydride, glycidyl allyl ether, vinyl glycidyl ether.
The preferred compound of formula I, II and IV is toxilic acid, maleic anhydride and (methyl) acrylate comprising epoxide group, such as glycidyl acrylate and glycidyl methacrylate; And with the ester of the tertiary alcohol, such as tert-butyl acrylate.Although the latter is without free carbonyl, their activity is close to the activity of free acid, and thus they are called as the monomer with potential carbonyl.
Multipolymer is advantageously made up of following material: the ethene of 50 to 98% weight, 0.1 to 20 % by weight comprise the monomer of epoxide group and/or methacrylic acid and/or comprise the monomer of anhydride group, and remaining amount is (methyl) acrylate.
Particularly preferred multipolymer is made up of following material
-50 to 98 % by weight, the particularly ethene of 55 to 95 % by weight,
-0.1 to 40 % by weight, particularly 0.3 to 20 % by weight glycidyl acrylate and/or glycidyl methacrylate, (methyl) vinylformic acid and/or maleic anhydride, and
-1 to 45 % by weight, particularly 10 to 40 % by weight n-butyl acrylate and/or 2-ethylhexyl acrylate.
Other preferred (methyl) acrylate are (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isobutyl acrylate and (methyl) tert-butyl acrylate.
Except these, also spendable other materials is vinyl acetate as comonomer and Vinyl Ether.
Above-mentioned ethylene copolymer, by known method preparation itself, is prepared preferably by random copolymerization effect at elevated pressures and temperatures.Suitable method is well-known.
Other preferred elastomericss are emulsion polymer, and its preparation method is such as described in the monograph " Emulsion polymerization " write by Blackley.Spendable emulsifying agent and catalyzer are that itself is known.
In principle, can use the elastomerics with uniform texture or those there is the elastomerics of shell structure.Shell structure depends on the order of addition of each monomer; The form of polymkeric substance is also by the impact of order of addition.
The only representative monomer for the preparation of elastomeric rubber part herein can mentioned is acrylate, such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylic ester, divinyl and isoprene, and their mixture.These monomers can with other monomers, such as, vinylbenzene, vinyl cyanide, Vinyl Ether and with other acrylate or methacrylic ester (such as methyl methacrylate, methyl acrylate, ethyl propenoate or propyl acrylate) copolymerization.
Elastomeric soft phase or rubber phase (second-order transition temperature is below 0 DEG C) can be core, shell or middle case (in the elastomeric situation that structure has more than two shells).The elastomerics with more than one shell also can have the shell that two or more is made up of rubber phase.
Except rubber phase, if also comprise more than one hard components (second-order transition temperature is more than 20 DEG C) in elastomer structure, so they are usually prepared as the vinylbenzene of principal monomer, vinyl cyanide, methacrylonitrile, alpha-methyl styrene, p-methylstyrene or acrylate or methacrylic ester (such as methyl acrylate, ethyl propenoate, methyl methacrylate) by polymerization.Except these elastomericss, also can use other comonomers of relatively small proportion at this.
Confirm that the emulsion polymer using surface to have active group is in some cases favourable.The example of this kind of group is epoxy group(ing), carboxyl, potential carboxyl, amino and amide group, and the functional group introduced by using the monomer of following general formula simultaneously
Wherein substituently to be defined as follows:
R
10for hydrogen or C
1-C
4-alkyl,
R
11for hydrogen or C
1-C
8-alkyl or aryl, is in particular phenyl,
R
12for hydrogen, C
1-C
10-alkyl, C
6-C
12-aryl or-OR
13,
R
13for C
1-C
8-alkyl or C
6-C
12-aryl, it can optionally be replaced by the group containing O or N,
X is chemical bond, C
1-C
10-alkylidene group or C
6-C
12-arylidene, or
Y is O-Z or NH-Z, and
Z is C
1-C
10-alkylidene group or C
6-C
12-arylidene.
The grafted monomer be described in EP-A 208 187 is also adapted at surface and introduces active group.
Other examples that can mention are acrylamide, the acrylate of Methacrylamide and replacement or methacrylic ester, such as, methacrylic acid (N-tert-butylamino) ethyl ester, vinylformic acid (N, N-dimethyl-amino) ethyl ester, vinylformic acid (N, N-dimethylamino) methyl esters and vinylformic acid (N, N dimethylamine base) ethyl ester.
The particle of rubber phase also can be through crosslinked.The example of cross-linking monomer is 1,3-divinyl, Vinylstyrene, diallyl phthalate and vinylformic acid dihydro DCPA (dihydrodicyclopentadienyl acrylate), and be described in the compound in EP-A 50 265.
Also can use the monomer being called as graft link monomer (graft-linking monomer), namely during polyreaction with different rates reaction the monomer with two or more polymerizable double bond.This compounds of preferred use: wherein at least one active group is polymerized with the speed almost identical with other monomers, and such as other active groups (or active group group) rate of polymerization is obviously slower.Different rates of polymerization can produce a certain proportion of unsaturated double-bond in rubber.If subsequently by another grafted branches on this kind of rubber, reacting with grafted monomer at least partially of the double bond so existed in rubber forms chemical bond, is namely chemically bound at least to a certain extent to graft base by the phase of grafting.
The example of this kind of graft link monomer is for comprising allylic monomer, be in particular the allyl ester of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate(AMA), diallyl maleate, diallyl fumarate and diallyl itaconate, and the corresponding monoallyl compound of these dicarboxylic acid.Except these graft link monomer, also have other suitable graft link monomer various.Details about this can see such as US-A 4 148 846.
The ratio of these cross-linking monomers in impact resistant modified polymers is generally nearly 5 % by weight, and preferably at the most 3 % by weight, with anti-impact modifier polymer weight.
Some preferred emulsion polymers are as shown in the table.At this, first can mention the graftomer with core and at least one shell, it has following structure:
These graftomer (special ABS and/or ASA polymkeric substance) (optionally with nearly 40 % by weight polyethylene terephthalate mixture in) preferably with nearly 40 % by weight amount be used for impact modification PBT.This kind of blended (blend) product can available from trade name
s (is from BASF AG's before
s).
Replace the graftomer in structure with more than one shell, also can use the elastomerics be made up of 1,3-butadiene, isoprene and n-butyl acrylate or their multipolymer of homogeneity (i.e. monoshell).These products are also prepared by using cross-linking monomer or have the monomer of active group simultaneously.
The example of preferred emulsion polymer is n-butyl acrylate/(methyl) acrylic copolymer, n-butyl acrylate/glycidyl acrylate multipolymer or n-butyl acrylate/glycidyl methacrylate copolymer, have the inner core that is made up of n-butyl acrylate or have a graftomer of the shell be made up of above-mentioned multipolymer based on divinyl, and ethene and provide the multipolymer of comonomer of active group.
Described elastomerics is also prepared by the method for other routines, such as, prepared by suspension polymerization.
Equally preferably be described in the silicon rubber in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290.
Certainly, the mixture of above-mentioned rubber type can also be used.
Thermoplastic composition of the present invention can comprise conventional processing aid (such as, reagent, lubricant, the releasing agent of stablizer, oxidation retarder, suppression thermal degradation and ultraviolet light degradation), tinting material (such as, dyestuff and pigment), nucleator, softening agent etc. are as component E).
The oxidation retarder that can mention and the example of thermo-stabilizer are for having sterically hindered phenols and/or phosphorous acid ester, Resorcinol, secondary aromatic amine (such as, pentanoic), the various substituents of these groups, and their mixture, its concentration reaches 1 % by weight, with the weighing scale of thermoplastic composition.
The UV stablizer that can mention be the Resorcinol of various replacement, salicylate, benzotriazole and benzophenone, its usage quantity usually nearly 2 % by weight, in moulding compound.
Addible tinting material is mineral dye, such as, and titanium dioxide, ultramarine (ultramarineblue), ferric oxide and carbon black; And pigment dyestuff, such as, (quinacridone) is with perylene for phthalocyanine (phthalocyanine), quinacridone; And dyestuff, such as, nigrosine (nigrosine) and Anthraquinones (anthraquinones).
Spendable nucleator is phenyl-phosphonite sodium, aluminum oxide, silicon-dioxide and preferably talc powder.
Usual use reaches other lubricants and the releasing agent of the amount of 1 % by weight.Preferred longer chain fatty acid (such as, stearic acid or docosoic acid), their salt (such as, calcium stearate or Zinic stearas) or montanin wax (montan waxe) (there is the mixture of the straight chain saturated carboxylic acid of 28 to 32 carbon atom chain lengths) or montanic acid calcium and montanic acid sodium or low-molecular-weight polyethylene wax or low-molecular-weight Poly Propylene Wax.
The example of the softening agent that can mention is phthalic acid dioctyl ester, phthalic acid dibenzyl ester, butyl benzyl phthalate, hydrocarbon ils and N-(normal-butyl) Phenylsulfonic acid amine.
Moulding compound of the present invention also can comprise 0 to 2 % by weight containing fluoroethylene polymer.These polyvinyl Oil repellent are 55 to 76 % by weight, preferably 70 to 76 % by weight.
These fluorine-containing polyvinyl examples be tetrafluoroethylene (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer and there is relatively low ratio (usually nearly 50 % by weight) can the TFE copolymer of ethylenically unsaturated monomer of copolymerization.These are such as described in " the Vinyl and Related Polymers " that edited by Schildknecht containing fluoroethylene polymer, Wiley-Verlag, 1952, in 484-494 page and " Fluoropolymers " (Wiley Interscience, 1972) of being edited by Wall.
These are evenly distributed in moulding compound containing fluoroethylene polymer, and preferably have at 0.05 to 10 μm, the particle diameter d particularly within the scope of 0.1 to 5 μm
50(mean value).These small particle size can particularly preferably obtain by using fluorine-containing polyvinyl aqueous dispersions and being incorporated in polyester fondant.
Thermoplastic composition of the present invention is by known method itself, by mixing starting ingredient in the mixing device (such as screw extruder, Brabender mixing machine or Banbury mixing machine) of routine, then it extruded and prepare.Extrudate can be cooled and pulverize.Also can each component of pre-mixing, then add separately remaining starting material and/or also can add remaining starting material as a mixture.Mixing temperature is generally 230 to 290 DEG C.
In another preferred working method, B component) and C) and optional D) and E) can mix with prepolymer, compounding and granulation.Subsequently under an inert atmosphere, lower than component A) fusing point temperature under, continuously or in batches solid phase compression is carried out to the particle of gained, until reach required viscosity.
The feature of polyester molding compounds of the present invention is excellent flame retardant resistance and relative low smoke density and heat release rate.The amount of the residue after burning increases.
The moulded product prepared by thermoplastic composition of the present invention or work in-process can such as automobile industry, electric utility, electronic industry, telecommunications industry, Information Technology Industry, the consumer electronics industries, or computer industry, or the vehicles strengthen article and the Constracture unit of flame retardant resistance with other transportation means, boats and ships, spacecraft, civilian department, office equipment, physical culture, medicine and usual requirement.
Some examples are as follows: plug-in type connector, plug, male component, core of a cable (cable-harness) parts, circuit handle seat, circuit handle base member, three-dimensional injection moulding circuit handle seat, electrical connector assembly and electromechanical integration parts.
Embodiment
Employ following component:
Component A): limiting viscosity IV is the polybutylene terephthalate of 107ml/g, and described viscosity (uses purchased from BASF SE's according to DIN 53728/ISO
b2550), at 25 DEG C, measure in phenol/orthodichlorobenzene (1:1) solution of 0.5 % by weight.
B component): in PBT 50% red phosphorus Masterbatch.
Component C1): polyacrylonitrile homopolymer
Mw:313400g/mol, it, according to DIN 55672-2:2008-06, utilizes GPC, part 2, PMMA standard and measuring
Component C2): polyacrylonitrile homopolymer
Mw:156000g/mol, it, according to DIN 55672-2:2008-06, utilizes GPC, part 2, PMMA standard and measuring
Component C3): polyacrylonitrile copolymer (for contrast)
Poly-(vinylidene chloride-altogether-vinyl cyanide), 80/20, CAS:9010-76-8
Component C4): styrene-acrylonitrile copolymer (for contrast)
The vinyl cyanide of 24% and the cinnamic random copolymers of 76%
Component D1): the mean thickness for polyester is the standard short glass fiber of 10 μm
Component E): pentaerythritol tetrastearate
The preparation of moulding compound and moulded product
Compounding (compounding) is adopted to manufacture suitable plastic composition.For this reason, each component mixes with the turnout of 20kg/h at about 270 DEG C in ZSK 26 twin screw extruder of homogeneous temperature distribution, discharges with the form of wire rod (strand), and cooling until can granulation, and carries out granulation.Under the die temperature of the temperature of fusion of about 260 DEG C and about 80 DEG C, for sample injection moulding in Arburg 420 DEG C of injection moulding machines of test listed in Table.
Measure mechanical property according to ISO 527-2/1A/5, and measure summer ratio (Charpy) shock resistance according to ISO 179-2/1eU (unnotched).
The fire resistance of 0.8mm sample is measured according to UL 94.
Smoke density, heat release amount is measured according to ISO 5660-1:2002, and the resistates after burning.
Following table shows the composition of moulding compound and the result of measurement.
Table 1
When * extruding, material decomposes, and does not obtain product
Table 2-4
Claims (7)
1. a thermoplastic composition, comprising:
A) thermoplastic polyester of 10 to 97 % by weight,
B) red phosphorus of 0.1 to 60 % by weight,
C) polyacrylonitrile homopolymer of 1 to 25 % by weight,
D) 0 to 50 % by weight threadiness or particulate fillers, and
E) other additives of 0 to 60 % by weight,
Wherein A) to E) total weight percent be 100%.
2. thermoplastic composition according to claim 1, comprising:
A) 10 to 97 % by weight
B) 0.5 to 40 % by weight
C) 1 to 15 % by weight
D) 1 to 50 % by weight
E) 0 to 50 % by weight.
3. the thermoplastic composition described in claim 1 or 2, comprising:
A) 20 to 95 % by weight
B) 0.5 to 40 % by weight
C) 1 to 15 % by weight
D) 5 to 45 % by weight
E) 0 to 30 % by weight.
4. the thermoplastic composition described in claims 1 to 3, wherein according to DIN55672-2:2008-06, the component C that second section (GPC standard P MMA) measures) average molecular weight Mw be 10000 to 400000.
5. the thermoplastic composition described in Claims 1-4, wherein component C) with the form of particle, powder, sheet, block and other component A) and B) and optional D) and E) to mix, then compounding.
6. the thermoplastic composition described in claim 1 to 5 is for the manufacture of the purposes of fiber, paper tinsel and moulded product.
7. fiber, paper tinsel or the moulded product that can be obtained by the thermoplastic composition described in claim 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12172386 | 2012-06-18 | ||
| EP12172386.0 | 2012-06-18 | ||
| PCT/EP2013/061996 WO2013189779A1 (en) | 2012-06-18 | 2013-06-11 | Flame-proof polyester comprising polyacrylonitrile homopolymerisates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104379669A true CN104379669A (en) | 2015-02-25 |
Family
ID=48607263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380032222.5A Pending CN104379669A (en) | 2012-06-18 | 2013-06-11 | Flame-proof polyester comprising polyacrylonitrile homopolymerisates |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2861665A1 (en) |
| JP (1) | JP2015520280A (en) |
| KR (1) | KR20150023271A (en) |
| CN (1) | CN104379669A (en) |
| BR (1) | BR112014028168A2 (en) |
| WO (1) | WO2013189779A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009589A (en) * | 2016-06-15 | 2016-10-12 | 安徽弘美电器有限公司 | Wire harness binder special for car and production process of wire harness binder |
| CN109735065A (en) * | 2018-12-28 | 2019-05-10 | 武汉融科包装材料有限公司 | Packaging steel coils halogen-free flameproof regenerative PET sheet material PP Pipe Compound and preparation method thereof |
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| US20010007888A1 (en) * | 1999-12-28 | 2001-07-12 | Takayuki Asano | Flame retardant resin composition |
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- 2013-06-11 CN CN201380032222.5A patent/CN104379669A/en active Pending
- 2013-06-11 BR BR112014028168A patent/BR112014028168A2/en not_active IP Right Cessation
- 2013-06-11 JP JP2015517673A patent/JP2015520280A/en not_active Withdrawn
- 2013-06-11 WO PCT/EP2013/061996 patent/WO2013189779A1/en active Application Filing
- 2013-06-11 KR KR20147032500A patent/KR20150023271A/en not_active Application Discontinuation
- 2013-06-11 EP EP13728184.6A patent/EP2861665A1/en not_active Withdrawn
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| JPH05255598A (en) * | 1992-03-11 | 1993-10-05 | Asahi Chem Ind Co Ltd | Flame-retardant high-impact resin composition |
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| CN106009589A (en) * | 2016-06-15 | 2016-10-12 | 安徽弘美电器有限公司 | Wire harness binder special for car and production process of wire harness binder |
| CN109735065A (en) * | 2018-12-28 | 2019-05-10 | 武汉融科包装材料有限公司 | Packaging steel coils halogen-free flameproof regenerative PET sheet material PP Pipe Compound and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150023271A (en) | 2015-03-05 |
| JP2015520280A (en) | 2015-07-16 |
| BR112014028168A2 (en) | 2019-09-24 |
| EP2861665A1 (en) | 2015-04-22 |
| WO2013189779A1 (en) | 2013-12-27 |
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