CN104804430B - A kind of polyamide moulding composition - Google Patents

Abstract

The invention discloses a polyamide molding composition, comprising the following composition: a, 30wt%-99.9wt% polyamide resin with pH value less than 7 in phenol; b, 0-70wt% reinforcing filler; c, 0-70wt% additives and/or other polymers; wherein, the sum of the percentages by weight of the three components a, b, and c is 100wt%; said polyamide resin with a pH value of less than 7 in phenol, based on polyamide The molar content of all carbon atoms in the amide resin, the molar content of bio-based carbon is above 40 mol%. Due to the use of polyamide resins with a specific molar content of bio-based carbon and a pH of less than 7 in phenol, polyamide molding compositions prepared from them have a lower melting weight loss τ , which means that they outgas less Less, the surface of the product is good when used for injection molding. Simultaneously, the Ganz whiteness W of embodiment product is higher, and color is better.

Description

A polyamide molding composition

technical field

The invention relates to the field of polymer materials, in particular to a polyamide molding composition.

Background technique

Polyamide is widely used for its good comprehensive properties, including mechanical properties, heat resistance, wear resistance, chemical resistance and self-lubricating properties, low coefficient of friction, and certain flame retardancy. Glass fiber and other fillers are filled to enhance and modify, improve performance and expand application range, etc. In recent years, semi-aromatic polyamides have been focused on development due to their better heat resistance and mechanical properties.

However, the existing polyamide resins mainly use raw materials from petroleum cracking products in the synthesis process. Petroleum is non-renewable, and the synthesis of these raw materials requires a complex chemical process, which consumes a lot of energy and produces many by-products that cause environmental pollution. This polyamide contains some gas volatiles, which will gradually emit during use. out, affecting the health of users. If polyamide is used in the field of food contact, the content of gas volatiles in the polyamide composition needs to be reasonably controlled.

Now, the end group test of polyamide resin has become a common method in this industry, which is used to characterize the number average molecular weight, reaction degree and other information of polyamide. Although the polyamide end groups may affect the pH of the solution, this is not the only important factor. The rigidity of different polyamide molecular chains, the concentration of amide groups, the second Veliy coefficient, the Huggins parameter, the θ solvent behavior, etc. will have a significant impact on its pH value. Even for polyamides with the same composition and monomer ratio, due to the joint action of the above factors, the pH value may vary greatly, resulting in differences in polymer properties.

The inventors have found through a large number of experiments that, on the basis of controlling the polyamide resin biobase to a specific molar content, and simultaneously selecting a polyamide resin with a pH value of less than 7 in phenol, the polyamide molding composition thus prepared can be effectively Prevent the polymer from degrading and producing gas during the injection molding process, and then solve technical problems such as product flow marks and local whitening. At the same time, the color of the polyamide molding composition is improved.

Contents of the invention

In order to overcome the disadvantages and deficiencies of the prior art, it was an object of the present invention to provide a polyamide molding composition which generates less gas during injection molding and which has improved color properties.

The present invention is achieved through the following technical solutions:

A polyamide molding composition comprising the following components:

a, 30wt%-99.9wt% polyamide resin with pH value less than 7 in phenol;

b, 0-70wt% reinforcing filler;

c, 0-70wt% additives and/or other polymers;

Wherein, the sum of the weight percentages of the three components a, b, and c is 100wt%.

Preferably, a polyamide molding composition comprising the following composition:

a, 30wt%-93wt% polyamide resin;

b. 1wt%-66wt% reinforcing filler;

c, 0.1wt%-59wt% additives and/or other polymers;

Wherein, the sum of the weight percentages of the three components a, b, and c is 100wt%.

In the polyamide resin with a pH value of less than 7 in phenol, based on the molar content of all carbon atoms in the polyamide resin, the molar content of bio-based carbon is above 40mol%; the molar content of bio-based carbon is according to ASTM standard D6866 -12/Method-B Measured.

The polyamide resin with a pH value of less than 7 in phenol preferably exhibits a pH value in phenol: 1≤pH≤6; more preferably 2≤pH≤5.

Preferably, in the polyamide resin having a pH value of less than 7 in phenol, based on the molar content of all carbon atoms in the polyamide resin, the molar content of bio-based carbon is above 50 mol%.

In the polyamide resin having a pH value of less than 7 in phenol, based on the mole fraction of all repeating units derived from diacids, at least 20 mol% of the repeating units are derived from terephthalic acid and/or 1,4-cyclohexane Diformic acid.

In the polyamide resin having a pH value of less than 7 in phenol, based on the mole fraction of all repeating units derived from diamine, at least 20 mol% of the repeating units are derived from 1,6-hexanediamine and/or 1,10- decyl diamine.

The content of the component b is preferably 10wt%-50wt%, more preferably 15wt%-40wt%;

If the content of the reinforcing filler is too low, the mechanical properties of the polyamide molding composition will be poor; if the content of the reinforcing filler is too high, the surface of the product of the polyamide molding composition will be seriously floating, which will affect the appearance of the product.

The shape of the reinforcing filler is fibrous, its average length is 0.01mm-20mm, preferably 0.1mm-6mm; its aspect ratio is 5:1-2000:1, preferably 30:1-600:1, when When the content of the fibrous reinforcing filler is within the above-mentioned range, the polyamide molding composition exhibits a high heat distortion temperature and increased high-temperature rigidity.

The reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler;

The inorganic reinforcing filler is selected from glass fibers, potassium titanate fibers, metal clad glass fibers, ceramic fibers, wollastonite fibers, metal carbide fibers, metal solidified fibers, asbestos fibers, alumina fibers, silicon carbide fibers, One or more of gypsum fibers or boron fibers, preferably glass fibers;

The use of glass fibers not only improves the moldability of polyamide molding compositions, but also improves mechanical properties such as tensile strength, flexural strength and flexural modulus, and improves heat resistance such as thermoplastic resin compositions when molded. Heat distortion temperature.

The organic reinforcing filler is selected from aramid fibers and/or carbon fibers.

The shape of the reinforcing filler is non-fibrous, such as powder, granule, plate, needle, fabric or felt, and its average particle size is 0.001 μm-100 μm, preferably 0.01 μm-50 μm.

When the average particle size of the reinforcing filler is less than 0.001 μm, it will lead to poor melt processability of the polyamide resin; when the average particle size of the reinforcing filler is greater than 100 μm, it will cause poor surface appearance of injection molded products.

The average particle size of the above-mentioned reinforcing filler is determined by an adsorption method, which can be selected from potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, Pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate, aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, One or more of calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide.

These reinforcing fillers can be hollow; in addition, for swelling phyllosilicates such as bentonite, montmorillonite, hectorite, and synthetic mica, organic ammonium salts can be used to exchange cations for interlayer ions. Montmorillonite.

In order to obtain better mechanical properties of the polyamide molding composition, the inorganic reinforcing filler can be functionally treated with a coupling agent.

Wherein the coupling agent is selected from isocyanate compounds, organosilane compounds, organotitanate compounds, organoborane compounds, epoxy compounds; preferably organosilane compounds;

Wherein, the organosilane compound is selected from alkoxysilane compounds containing epoxy groups, alkoxysilane compounds containing mercapto groups, alkoxysilane compounds containing urea groups, alkoxysilane compounds containing isocyanate groups, One or more of alkoxysilane compounds containing terminal amino groups, alkoxysilane compounds containing hydroxyl groups, alkoxysilane compounds containing carbon-carbon unsaturated groups, and alkoxysilane compounds containing acid anhydride groups.

The alkoxysilane compound containing epoxy group is selected from γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4- One or more of epoxycyclohexyl)ethyltrimethoxysilane;

The mercapto-containing alkoxysilane compound is selected from γ-mercaptopropyltrimethoxysilane and/or γ-mercaptopropyltriethoxysilane;

The ureido-containing alkoxysilane compound is selected from γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-(2-ureidoethyl) terminal aminopropyl One or several kinds of trimethoxysilane;

The alkoxysilane compound containing isocyanate group is selected from γ-isocyanate propyltriethoxysilane, γ-isocyanate propyltrimethoxysilane, γ-isocyanate propylmethyldimethoxysilane, γ-Isocyanatopropylmethyldiethoxysilane, γ-Isocyanatopropylethyldimethoxysilane, γ-Isocyanatopropylethyldiethoxysilane, γ-Isocyanatopropyltrichloro One or more silanes;

The alkoxysilane compound containing terminal amino group is selected from γ-(2-terminal aminoethyl) terminal aminopropylmethyldimethoxysilane, γ-(2-terminal aminoethyl) terminal One or more of aminopropyltrimethoxysilane and γ-terminal aminopropyltrimethoxysilane;

The hydroxyl-containing alkoxysilane compound is selected from γ-hydroxypropyltrimethoxysilane and/or γ-hydroxypropyltriethoxysilane;

The alkoxysilane compound containing carbon-carbon unsaturated group is selected from γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β-(N-vinylbenzyl One or several types of aminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride;

The alkoxysilane compound containing acid anhydride group is selected from 3-trimethoxysilylpropyl succinic anhydride;

The organosilane compound is preferably γ-methacryloxypropyltrimethoxysilane, γ-(2-terminal aminoethyl) terminal aminopropylmethyldimethoxysilane, γ-( 2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, or 3-trimethoxysilylpropylsuccinic anhydride.

The above-mentioned organosilane compound can be used to treat the surface of the inorganic reinforcing filler according to a conventional method, and then it is melt-kneaded with the polyamide resin to prepare the polyamide molding composition.

It is also possible to directly add organosilane compounds for in-situ blending at the same time as the inorganic reinforcing filler and polyamide resin are melted and kneaded.

Wherein, the amount of the coupling agent is 0.05wt%-10wt% relative to the weight of the inorganic reinforcing filler, preferably 0.1wt%-5wt%.

When the amount of coupling agent is less than 0.05wt%, it cannot achieve obvious effect of improving mechanical properties; when the amount of coupling agent is greater than 10wt%, the inorganic reinforcing filler is prone to agglomeration and poor dispersion in polyamide resin risk, which eventually leads to a decrease in mechanical properties.

The additive is selected from one or more of flame retardants, impact modifiers, other polymers, and processing aids; the other polymers are preferably aliphatic polyamides, polyolefin homopolymers, ethylene-α- One or more of olefin copolymers and ethylene-acrylate copolymers; the processing aids are selected from antioxidants, heat-resistant stabilizers, weather-resistant agents, mold release agents, lubricants, pigments, dyes, plasticizers, One or more antistatic agents.

The flame retardant is a flame retardant or a combination of a flame retardant and a flame retardant assisting agent, based on the total weight of the polyamide molding composition, its content is preferably 10wt%-40wt%; the flame retardant content is too low to cause The flame retardant effect becomes worse, and the content of flame retardant is too high, which leads to the decline of the mechanical properties of the material.

The flame retardant is a halogenated flame retardant or a halogen-free flame retardant;

The halogen flame retardant is selected from brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated One or more of phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbrominated tricyclopentadecane or brominated aromatic cross-linked polymer, preferably bromine Polystyrene;

The halogen-free flame retardant is selected from one or more of nitrogen-containing flame retardants, phosphorus-containing flame retardants, or nitrogen- and phosphorus-containing flame retardants; phosphorus-containing flame retardants are preferred.

The phosphorus-containing flame retardant is selected from the group consisting of monophosphate aryl phosphate, diphosphate aryl phosphate, dimethyl alkyl phosphonate, triphenyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, acryl One or more of phenyl phosphate, butyl benzene phosphate or phosphinate; preferably phosphinate;

The phosphinate compound is represented by, for example, compounds represented by the following formulas I and/or II.

In formula I and formula II, R ¹ and R ² may be the same or different, and represent linear or branched C1-C6-alkyl, aryl or phenyl, respectively. R ³ represents straight-chain or branched C1-C10-alkylene, C6-C10-arylene, C6-C10-alkylarylene, C6-C10-arylalkylene. M represents a calcium atom, a magnesium atom, an aluminum atom and/or a zinc atom. m is 2 or 3, n is 1 or 3, and x is 1 or 2.

More specific examples of phosphinate compounds include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate , magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, diethylphosphinic acid Aluminum, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, Methanebis(methylphosphinate) calcium, methanebis(methylphosphinate) magnesium, methanebis(methylphosphinate) aluminum, methanebis(methylphosphinate) zinc, benzene-1,4 -(dimethylphosphinate) calcium, benzene-1,4-(dimethylphosphinate) magnesium, benzene-1,4-(dimethylphosphinate) aluminum, benzene-1,4-( Dimethylphosphinate) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, diphenylphosphinate calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate, etc., preferably calcium dimethylphosphinate, aluminum dimethylphosphinate, dimethylphosphinate Zinc acid, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, diethyl Zinc phosphinate, more preferably aluminum diethylphosphinate.

Phosphinate compounds as flame retardants are readily available on the market. Examples of commercially available phosphinate compounds include EXOLIT OP1230, OP1311, OP1312, OP930, OP935 and the like manufactured by Clariant.

In the polyamide molding composition of the present invention comprising the polyamide resin described above, based on the total weight of the polyamide molding composition, the additive component may further comprise up to 45% by weight of one or more impact modifiers; Preferably it is 5wt%-30wt%.

Wherein, the impact modifier can be natural rubber, polybutadiene, polyisoprene, polyisobutylene, butadiene and/or isoprene and styrene or with styrene derivatives and with other copolymers Copolymers of monomers, hydrogenated copolymers, and/or copolymers prepared by grafting or copolymerization with anhydrides, (meth)acrylic acid or their esters; the impact modifier can also be a cross-linked elastomer Grafted rubber of a core, the cross-linked elastomeric core is composed of butadiene, isoprene or alkyl acrylate, and has a grafted shell composed of polystyrene or can be non-polar or polar olefins Polymers or copolymers, such as ethylene-propylene rubber, ethylene-propylene-diene rubber, or ethylene-octene rubber, or ethylene-vinyl acetate rubber, or by grafting or with anhydrides, (meth)acrylic acid or their esters non-polar or polar olefin homopolymers or copolymers obtained by copolymerization; the impact modifier can also be a carboxylic acid functionalized copolymer such as poly(ethylene-co-(meth)acrylic acid) or poly (ethylene-1-alkene-co-(meth)acrylic acid), where the 1-alkene is an alkene or an unsaturated (meth)acrylate having more than 4 atoms, including acid groups neutralized by metal ions to To some extent those copolymers.

Impact modifiers based on styrene monomers (styrene and styrene derivatives) and other vinyl aromatic monomers, block copolymers of alkenyl aromatic compounds and conjugated dienes, and Hydrogenated block copolymers of alkenyl aromatic compounds and conjugated dienes, and combinations of these types of impact modifiers. The block copolymers comprise at least one block a derived from an alkenylaromatic compound and at least one block b derived from a conjugated diene. In the case of hydrogenated block copolymers, the proportion of aliphatically unsaturated carbon-carbon double bonds is reduced by hydrogenation. Suitable block copolymers are di-, tri-, tetra- and multi-block copolymers with a linear structure. However, branched and star structures can also be used according to the invention. Branched block copolymers are obtained in a known manner, for example by grafting polymer "side branches" onto the polymer backbone.

Other alkenylaromatic compounds that can be used with styrene or in mixtures with styrene are vinyl substituted by C1-20 hydrocarbyl groups or by halogen atoms on the aromatic ring and/or on the C=C double bond aromatic monomers.

Examples of alkenyl aromatic monomers are styrene, p-methylstyrene, α-methylstyrene, ethylstyrene, tert-butylstyrene, vinyltoluene, 1,2-diphenylethylene, 1,1-diphenylethylene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, and chlorostyrene, and combinations thereof. Styrene, p-methylstyrene, α-methylstyrene, and vinylnaphthalene are preferred.

Preference is given to using styrene, α-methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinyltoluene, 1,2-diphenylethylene, 1,1-diphenylethylene , or a mixture of these substances. Particular preference is given to using styrene. However, alkenylnaphthalene can also be used.

Examples of diene monomers that can be used are 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3 - Pentadiene, 1,3-hexadiene, isoprene, chloroprene and piperylene. Preference is given to 1,3-butadiene and isoprene, especially 1,3-butadiene (hereinafter denoted by the abbreviated form butadiene).

The alkenyl aromatic monomers used preferably comprise styrene and the diene monomers used preferably comprise butadiene, which means that styrene-butadiene block copolymers are preferred. The block copolymers are generally prepared in a manner known per se by anionic polymerization.

In addition to styrene monomers and diene monomers, other additional monomers may also be used concomitantly. The proportion of comonomers is preferably 0-50% by weight, particularly preferably 0-30% by weight, particularly preferably 0-15% by weight, based on the total amount of monomers used. Examples of suitable comonomers are acrylates, especially C1-C12 alkyl acrylates, such as n-butyl acrylate or 2-ethylhexyl acrylate, and methacrylates, especially C1-C12 methacrylates, respectively. Alkyl esters such as methyl methacrylate (MMA). Other possible comonomers are (meth)acrylonitrile, glycidyl (meth)acrylate, vinyl methyl ether, diallyl and divinyl ethers of glycols, divinylbenzene and vinyl acetate ester.

In addition to conjugated dienes, the hydrogenated block copolymers also contain, if appropriate, lower hydrocarbon moieties such as ethylene, propylene, 1-butene, dicyclopentadiene or non-conjugated dienes. The proportion of unreduced aliphatic unsaturation originating from block b in the hydrogenated block copolymer is less than 50%, preferably less than 25%, especially less than 10%. The aromatic moieties derived from block a are reduced to an extent of up to 25%. By hydrogenation of styrene-butadiene copolymer and hydrogenation of styrene-butadiene-styrene copolymer, a hydrogenated block copolymer, namely styrene-(ethylene-butylene) diblock copolymer and benzene Ethylene-(ethylene-butylene)-styrene triblock copolymer.

The block copolymer preferably comprises 20% to 90% by weight of block a, especially 50% to 85% by weight of block a. Dienes can be introduced into block b in 1,2-orientation or 1,4-orientation.

The molar mass of the block copolymer is 5000 g/mol to 500000 g/mol, preferably 20000 g/mol to 300000 g/mol, in particular 40000 g/mol to 200000 g/mol.

Suitable hydrogenated block copolymers are commercially available products such as (Kraton polymers) G1650, G1651 and G1652, and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141 and H1272.

Examples of non-hydrogenated block copolymers are polystyrene-polybutadiene, polystyrene-poly(ethylene-propylene), polystyrene-polyisoprene, poly(α-methylstyrene)-poly Butadiene, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly(ethylene-propylene)-polystyrene, polystyrene-polyisoprene-polystyrene, and Poly(alpha-methylstyrene) polybutadiene-poly(alpha-methylstyrene), and combinations thereof.

Suitable non-hydrogenated block copolymers are commercially available under the trade names (Phillips), (Shell), (Dexco) and (Kuraray).

In the polyamide molding composition of the present invention comprising the above-mentioned polyamide resin, the additive component may further comprise other polymers selected from the group consisting of aliphatic polyamides, polyolefin homopolymers or ethylene-α- Olefin copolymers, ethylene-acrylate copolymers.

The aliphatic polyamides include but are not limited to aliphatic diacids and aliphatic diamines derived from 4 to 20 carbon atoms, or lactams with 4 to 20 carbon atoms, or aliphatic polyamides with 4 to 20 carbon atoms. One or more of polymers of diacids, aliphatic diamines and lactams. Including but not limited to, polyhexamethylene adipamide (PA66), polycaprolactam (PA6), polyhexamethylene sebacamide (PA610), polydecanediamide sebacamide (PA1010), adipate-hexanediamide Amine-caprolactam copolymer (PA66/6), polyundecalactam (PA11), polylaurolactam (PA12), and mixtures of two or more thereof.

The ethylene-α-olefin copolymers are preferably EP elastomers and/or EPDM elastomers (ethylene-propylene rubber and ethylene-propylene-diene rubber, respectively). For example, the elastomer may comprise an elastomer based on ethylene-C3-C12-α-olefin copolymers containing 20 wt % to 96 wt %, preferably 25 wt % to 85 wt % ethylene, where C3 to C12-α-olefin copolymers are particularly preferred here. Olefins include olefins selected from propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and/or 1-dodecene, particularly preferably other polymers including ethylene-propylene One or more of rubber, LLDPE, VLDPE.

Alternatively or additionally (e.g. in a mixture), the other polymers may also comprise terpolymers based on ethylene-C3-C12-α-olefins and non-conjugated dienes, preferably containing 25wt% - 85wt% ethylene and up to a maximum of 10wt% non-conjugated dienes, particularly preferred here are C3-C12-α-olefins including those selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene , 1-octene, 1-decene and/or 1-dodecene alkenes, and/or wherein the non-conjugated dienes are preferably selected from bicyclo[2.2.1]heptadiene, 1,4-hexadiene Dienes, dicyclopentadiene and/or especially 5-ethylidene norbornene.

Ethylene-acrylate copolymers can also be used as constituents of the other polymers.

Other possible forms of said other polymers are respectively ethylene-butene copolymers and mixtures (blends) comprising these systems.

Preferably, the other polymers comprise components having anhydride groups, these by thermal reaction of the backbone polymer with an unsaturated dianhydride, with an unsaturated dicarboxylic acid, or with a monoalkyl ester of an unsaturated dicarboxylic acid or free radical reaction, introduced at a concentration sufficient to bind well to the polyamide, and here it is preferred to use a reagent selected from the group consisting of:

Maleic acid, maleic anhydride, monobutyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride. Preferably 0.1wt% - 4.0wt% of unsaturated acid anhydride is grafted onto the impact component as a component of C, or unsaturated dianhydride or its precursor is applied by grafting together with other unsaturated monomers. Usually the preferred degree of grafting is 0.1%-1.0%, particularly preferably 0.3%-0.7%. Another possible composition of other polymers is a mixture of ethylene-propylene copolymers and ethylene-butene copolymers, where the degree of maleic anhydride grafting (MA grafting degree) is 0.3% to 0.7%.

The abovementioned possible systems for the other polymers can also be used in the form of mixtures.

Furthermore, the additive component may contain components having functional groups such as carboxylic acid groups, ester groups, epoxy groups, oxazoline groups, carbodiimide groups, isocyanate groups , silanol groups, and carboxylate groups, or the additive component may contain a combination of two or more of the above functional groups. Monomers with such functional groups can be incorporated by copolymerization or grafting onto the elastomeric polyolefin.

Furthermore, impact modifiers based on olefinic polymers can also be modified by grafting with unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triacetylsilane, methacryloxypropyltrimethoxysilane, or acryltrimethoxysilane.

Elastomeric polyolefins are random, alternating or block copolymers with linear, branched or core-shell structures and contain functional groups that can react with provide sufficient compatibility.

Thus, the impact modifiers of the present invention include homopolymers or copolymers of olefins (e.g. ethylene, propylene, 1-butene), or olefins and copolymerizable monomers (e.g. vinyl acetate, (meth)acrylates, and methylhexadiene).

Examples of crystalline olefin polymers are low density, medium density and high density polyethylene, polypropylene, polybutadiene, poly-4-methylpentene, ethylene-propylene block copolymers, or ethylene-propylene random Copolymer, Ethylene-Methylhexadiene Copolymer, Propylene-Methylhexadiene Copolymer, Ethylene-Propylene-Butene Copolymer, Ethylene-Propylene-Hexene Copolymer, Ethylene-Propylene-Methylhexadiene Copolymer Copolymer, poly(ethylene-vinyl acetate) (EVA), poly(ethylene-ethyl acrylate) (EEA), ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene- Propylene-diene terpolymers, and combinations of the foregoing polymers.

Examples of commercially available impact modifiers that can be used in the additive component are:

TAFMER MC201: Blend of g-MA (-0.6%) 67% EP copolymer (20 mol% propylene) + 33% EB copolymer (15 mol% 1-butene)): Mitsui Chemicals, Japan.

TAFMER MH5010: g-MA (-0.6%) ethylene-butene copolymer; Mitsui.

TAFMER MH7010: g-MA (-0.7%) ethylene-butene copolymer; Mitsui.

TAFMER MH7020: g-MA (-0.7%) EP copolymer; Mitsui.

EXXELOR VA1801: g-MA (-0.7%) EP copolymer; Exxon Mobile Chemicals, US.

EXXELOR VA1803: g-MA (0.5-0.9%) EP copolymer, amorphous, Exxon.

EXXELOR VA1810: g-MA (-0.5%) EP copolymer, Exxon.

EXXELOR MDEX 941l: g-MA (0.7%) EPDM, Exxon.

FUSABOND MN493D: g-MA (-0.5%) ethylene-octene copolymer, DuPont, US.

FUSABOND A EB560D: (g-MA) ethylene-n-butyl acrylate copolymer, DuPont ELVALOY, DuPont.

Also preferred are ionic polymers in which the polymer-bonded carboxyl groups are all or to some extent bonded to each other through metal ions.

Particular preference is given to copolymers of butadiene and styrene functionalized with maleic anhydride grafts, nonpolar or polar olefin homopolymers and copolymers prepared by grafting with maleic anhydride, and carboxylic acid functionalized Copolymers, such as poly(ethylene-co(meth)acrylic acid) or poly(ethylene-co-1-olefin-co-(meth)acrylic acid), in which the acid groups have been partially neutralized by metal ions with.

In addition, various processing aids, such as antioxidants and/or heat-resistant stabilizers (hindered phenol-based, hydroquinone-based, Phosphites and their substitutes, copper halides, iodine compounds, etc.), weather resistance agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.) , release agent and lubricant (aliphatic alcohol, aliphatic amide, aliphatic bisamide, diurea and polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (niglosine, Nigrosine, etc.), plasticizers (octyl p-hydroxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents , polyoxyethylene sorbitan monostearate and other non-ionic antistatic agents, betaine-based amphoteric antistatic agents, etc.).

In order to obtain the molded article of the present invention, the polyamide resin or polyamide resin composition of the present invention can be molded by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, and film molding. These molded products can be molded into desired shapes, and can be used in resin molded products such as automobile parts and machine parts, and the like. As a specific application, it is useful in the following applications: automobile engine cooling water system components, especially radiator tank parts such as the top and bottom of the radiator tank, coolant storage tank, water pipes, water pump casings, water pump impellers, valves and other water pumps Components and other components used in contact with cooling water in the engine room of an automobile, such as switches, subminiature slide switches, DIP switches, switch casings, lamp holders, straps, connectors, connector casings, and connector casings , IC sockets, bobbins, bobbin covers, relays, relay boxes, capacitor casings, internal parts of motors, small motor casings, gear cams, balance wheels, gaskets, insulators, fasteners, buckles, clips, Bicycle wheels, casters, helmets, terminal blocks, electric tool casings, starter insulation parts, spoilers, tanks, radiator tanks, chamber tanks, liquid storage tanks, fuse boxes, air cleaners Housings, air conditioner fans, terminal housings, wheel covers, suction and exhaust pipes, bearing supports, cylinder head covers, intake manifolds, water pipe impellers, clutch release levers, speaker vibration plates, heat-resistant containers, microwave oven parts, Electric/electronic related parts represented by rice cooker parts, printer ribbon guides, etc., automobile/vehicle related parts, home appliances/office electrical parts, computer related parts, facsimile/copier related parts, machinery related parts, and other various uses.

Implementation

The molar content of the bio-based carbon is measured according to ASTM standard D6866-12/Method-B.

The test method for the relative viscosity of the obtained polyamide resin: refer to ^GB12006.1-89 , the method for determining the viscosity number of polyamide; the specific test method is: measure the concentration of 10 mg/ml poly The relative viscosity η _r of the amide;

The test method for the melting point of polyamide resin: refer to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; the specific test method is: use Perkin Elmer Diamond DSC analyzer to test the melting point of the sample; nitrogen atmosphere, flow rate is 40mL /min; during the test, the temperature was first raised to 340°C at 10°C/min, kept at 340°C for 2 minutes, then cooled to 50°C at 10°C/min, and then raised to 340°C at 10°C/min, and the endothermic The peak temperature is set as the melting _point Tm ;

pH measurement of polyamide resin: take 0.5000g polyamide resin, add 50mL of phenol, heat to reflux and cool to room temperature, use non-aqueous electrode to test its pH value.

Polyamide resin (molding composition) weight loss rate τ test during melting process:

Test the melting weight loss rate τ of polyamide resin (molding composition) to simulate the gas generated during injection molding. The specific test method is as follows -

After placing the polyamide resin (molding composition) in an oven at 130 ^o C for 4 hours, weigh 50.0000g of the polymer, put it into a 250ml three-neck bottle, and then put it into a mechanical stirring paddle. Weigh the total weight of the three-necked flask, the polymer and the mechanical stirring paddle, and record it as m ₀ . Connect the _N2 tube and the condensing device. Among them, the mechanical stirring blade adopts the IKA EUROSTAR 20 model product, and the setting stirring speed is 1500rpm. After raising the temperature to 30 ^o C above the melting point of the polyamide resin (molding composition) and keeping the temperature constant, immerse the above-mentioned three-necked bottle with the polyamide resin (molding composition) in an oil bath for 30 minutes. Then take out the three-neck bottle, wipe off the oil on the outer wall, and cool it down. Weigh the total weight of the three-necked flask, the polymer and the mechanical stirring paddle, and record it as m ₁ . Then polyamide resin (molding composition) melting weight loss rate τ = ( m ₀ - m ₁ )/50.0000×100%.

The test method for the color of the obtained polyamide resin (molding composition) product: use a swatch mold of 50*30*2mm, take 3000g of polymer particles for injection molding, and obtain a smooth swatch. Put the color plate on the Libao Color-Eye7000A computer color measuring instrument to obtain the W value of Ganz whiteness. This value can reflect the color of the polyamide resin (molding composition) product, and the higher the value, the better the color of the product.

The polyamide resin used in the present invention is prepared according to the following method:

In the autoclave equipped with magnetic coupling stirring, condenser, gas phase port, feed port, pressure explosion-proof port, add the reaction raw materials according to the ratio in the table; add sodium hypophosphite, benzoic acid and deionized water again; sodium hypophosphite weight is 0.1%-0.5% of the weight of other feeds except deionized water, the amount of benzoic acid is 2%-8% of the total amount of diacids, and the weight of deionized water is 20%-40% of the total weight of feed. Vacuumize and fill high-purity argon/carbon dioxide mixed gas as a protective gas to start the reaction. The temperature of the reaction mixture was raised to 220°C-230°C and stirred for 3-5 hours, then the valve was opened to slowly release the pressure and drain water while keeping the temperature and pressure constant. Drain until the drainage volume reaches 70% of the input deionized water volume. At this time, the temperature began to rise, and the temperature was raised to 250°C-270°C within 3 hours, and the temperature was kept constant for 2 hours. After the reaction is completed, the valve is opened to discharge the material to obtain a prepolymer.

Test the melting point of the prepolymer according to the method for testing the melting point of polyamide resin, and set it as T°C.

After the prepolymer was vacuum-dried at 80°C for 24 hours, the mixed gas of high-purity argon/carbon dioxide was used as a protective gas for solid-phase tackification, and the solid-phase tackification temperature was (T-50)°C. During the solid phase viscosification process, samples were continuously taken, and the final polymerization endpoint was determined by sampling the viscosity.

Resins with different bio-based contents and pH values can be obtained by reasonably adjusting the monomer composition in the above process and the ratio of the high-purity argon/carbon dioxide mixed gas used as the protective gas.

Table 1 shows the polyamide resins used in the present invention. The raw material monomers used in the present invention are all non-bio-based monomers unless otherwise specified. Bio-based monomers are limited to 1,10-decanediamine, 11-aminoundecanoic acid, and hexamethylenediamine in PA1, PA2, and PA3. The performance indicators of polyamide resin are as follows:

Table 1

diamine Diacid Lactam relative viscosity melting point pH Biobased carbon content/mol% PA1 1,6-Hexanediamine 100mol% Terephthalic acid 40mol%; adipic acid 40mol%; 1,4-cyclohexanedicarboxylic acid 20mol% 2.181 292 2.6 45 PA2 1,10-decanediamine 40mol%; 1,6-hexanediamine 60mol% Terephthalic acid 40mol%; adipic acid 60mol% 2.198 284 5.2 55 PA3 1,10-decanediamine 90mol%; 1,6-hexanediamine 10mol% Terephthalic acid 95mol%; adipic acid 5mol% 2.247 290 3.9 55 PA4 1,10-decanediamine 100mol% Terephthalic acid 100mol% Caprolactam 100mol% 2.263 256 4.5 42 PA5 1,6-Hexanediamine 100mol% Terephthalic acid 40mol%; adipic acid 40mol%; 1,4-cyclohexanedicarboxylic acid 20mol% 2.145 293 2.9 0 PA6 1,10-decanediamine 40mol%; 1,6-hexanediamine 60mol% Terephthalic acid 40mol%; adipic acid 60mol% 2.188 285 10.5 55

Examples 1-8 and Comparative Examples 1-5: Preparation of Polyamide Molding Compositions

Mix the polyamide resin, flame retardant and other additives uniformly in the high mixer according to the formula in Table 2-3, then feed them into the twin-screw extruder through the main feeding port, and feed the reinforcing filler through the side feeding scale , extruded, water cooled, granulated and dried to obtain the polyamide molding composition.

In table 2, the formulas in the following table are parts by weight

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 polyamide resin PA2 PA2 PA3 PA3 PA1 PA1 PA4 PA4 resin content 70 40 70 50 93 50 30 99.9 glass fiber 29 1 29 30 1 30 66 0 Phosphinate flame retardant 0 50 0 15 5 15 3 0 Polybutene 0 6 0 2 0 2 0 0 Dipentaerythritol 0 1 0 1 0 1 0 0 Zinc borate 0 1 0 1 0 1 0 0 Phenolic Antioxidants 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.05 polyethylene wax 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.05 τ/% 0.35 0.82 0.30 0.31 0.85 0.91 1.08 1.30 W 77.2 70.4 80.3 86.1 68.1 66.4 70.4 61.8

In table 3, the formulas in the following table are parts by weight

Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 polyamide resin PA5 PA5 PA6 PA6 PA6 resin content 70 50 70 50 30 glass fiber 29 30 29 30 69 Phosphinate flame retardant 0 15 0 15 0 Polybutene 0 2 0 2 0 Dipentaerythritol 0 1 0 1 0 Zinc borate 0 1 0 1 0 Phenolic Antioxidants 0.5 0.5 0.5 0.5 0.5 polyethylene wax 0.5 0.5 0.5 0.5 0.5 τ/% 2.11 3.45 2.28 3.55 2.0 W 30.5 27.2 33.1 30.2 33.2

It can be seen from Table 2-3 that due to the use of a polyamide resin with a specific molar content of bio-based carbon and a pH value of less than 7 in phenol, the melting weight loss rate τ of the polyamide molding composition prepared therefrom is relatively low. Low, which means that it releases less gas, and the surface of the product is good when used for injection molding. Simultaneously, the Ganz whiteness W of embodiment product is higher, and color is better.

Claims (24)

1. A polyamide molding composition comprising the following components: a, 30wt%-99.9wt% polyamide resin; b, 0-70wt% reinforcing filler; c, 0-70wt% flame retardants and/or other polymers; Wherein, the sum of the percentages by weight of the three components of a, b, and c is 100wt%; In the polyamide resin, based on the molar content of all carbon atoms in the polyamide resin, the molar content of the bio-based carbon is above 50mol%; the molar content of the bio-based carbon is measured according to ASTM standard D6866-12/Method-B ; The pH value of the polyamide resin in phenol presents: 1≤pH≤6; The polyamide resin, based on the mole fraction of all repeating units derived from diacids, has at least 20 mol% of repeating units derived from terephthalic acid and/or 1,4-cyclohexanedicarboxylic acid; In the polyamide resin, based on the mole fraction of all repeating units derived from diamine, at least 20 mol% of the repeating units are derived from 1,6-hexanediamine and/or 1,10-decanediamine. 2. A polyamide molding composition as claimed in claim 1, comprising the following composition: a, 30wt%-93wt% polyamide resin; b. 1wt%-66wt% reinforcing filler; c, 0.1wt%-59wt% flame retardants and/or other polymers; Wherein, the sum of the weight percentages of the three components a, b, and c is 100wt%. 3. The polyamide molding composition according to claim 1 or 2, characterized in that, the pH value of the polyamide resin in phenol exhibits: 2≤pH≤5. 4. The polyamide molding composition according to claim 1 or 2, characterized in that, the shape of the reinforcing filler is fibrous, and its average length is 0.01mm-20mm; its aspect ratio is 5:1- 2000:1; the content of the reinforcing filler is 10wt%-50wt%; the reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler, and the inorganic reinforcing filler is selected from glass fiber, potassium titanate fiber, ceramic fiber, silica fume One or more of stone fibers, metal carbide fibers, asbestos fibers, gypsum fibers, and boron fibers; the organic reinforcing filler is selected from aramid fibers and/or carbon fibers. 5. The polyamide molding composition according to claim 4, characterized in that the reinforcing filler has an average length of 0.1 mm to 6 mm. 6. The polyamide molding composition according to claim 4, characterized in that, the aspect ratio of the reinforcing filler is 30:1-600:1. 7. The polyamide molding composition according to claim 4, characterized in that, the content of the reinforcing filler is 15wt%-40wt%. 8. The polyamide molding composition according to claim 4, characterized in that the inorganic reinforcing filler is glass fiber. 9. Polyamide molding composition according to claim 8, characterized in that the glass fibers are metal-clad glass fibers. 10. The polyamide molding composition according to claim 4, wherein the ceramic fibers are silicon carbide fibers or alumina fibers. 11. The polyamide molding composition according to claim 1 or 2, wherein the reinforcing filler is non-fibrous in shape, has an average particle size of 0.001 μm-100 μm, and is selected from potassium titanate whiskers , zinc oxide whiskers, aluminum borate whiskers, wollastonite, zeolite, mica, talc, clay, pyrophyllite, synthetic mica, asbestos, aluminosilicate, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, One or more of calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide. 12. The polyamide molding composition according to claim 11, characterized in that the average particle size of the reinforcing filler is 0.01 μm-50 μm. 13. Polyamide molding composition according to claim 11, characterized in that the clay is bentonite or kaolin. 14. The polyamide molding composition according to claim 11, characterized in that the mica is sericite. 15. The polyamide molding composition according to claim 1 or 2, wherein the flame retardant is a halogenated flame retardant or a halogen-free flame retardant; the halogenated flame retardant is selected from bromine brominated polystyrene, brominated polyphenylene ether, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated poly One or more of carbonate, perbrominated tricyclopentadecane or brominated aromatic cross-linked polymer; the halogen-free flame retardant is selected from nitrogen-containing flame retardants, phosphorus-containing flame retardants or nitrogen-containing and One or more of phosphorus flame retardants; based on the total weight of the polyamide molding composition, the content of the flame retardants is 10wt%-40wt%. 16. The polyamide molding composition according to claim 15, characterized in that the flame retardant is a halogen-free flame retardant. 17. The polyamide molding composition according to claim 15, wherein the halogenated flame retardant is brominated polystyrene. 18. The polyamide molding composition according to claim 16, wherein the halogen-free flame retardant is a phosphorus-containing flame retardant. 19. The polyamide molding composition according to claim 15, wherein the brominated epoxy resin is a brominated bisphenol A type epoxy resin. 20. The polyamide molding composition according to claim 18, wherein the phosphorus-containing flame retardant is selected from the group consisting of aryl phosphate monophosphate, aryl phosphate diphosphate, dimethyl alkyl phosphonate , one or more of triphenyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, propylbenzene-based phosphate, butylbenzene-based phosphate, and phosphinate. 21. The polyamide molding composition according to claim 20, wherein the phosphorus-containing flame retardant is a phosphinate having the following structural formulas I and/or II: In formula I and formula II, R ¹ and R ² can be the same or different, respectively represent straight-chain or branched C1-C6-alkyl, aryl; R ³ represents straight-chain or branched C1 -C10-alkylene, C6-C10-arylene; M represents calcium atom, magnesium atom, aluminum atom and/or zinc atom; m is 2 or 3, n is 1 or 3, x is 1 or 2. 22. The polyamide molding composition according to claim 21, characterized in that R ³ is a C6-C10-alkylarylene group. 23. The polyamide molding composition according to claim 21, characterized in that the aryl group is phenyl. 24. The polyamide molding composition according to claim 21, characterized in that R ³ is C6-C10-arylalkylene.