Polymer Additive, Flame Retardant, Polymer Molding Material, and Preparation Method and Application Thereof

Abstract

The present invention discloses a polymer additive, a flame retardant, a polymer molding material, and a preparation method and application thereof. The polymer additive includes: aluminum diethylphosphinate and aluminum ethylbutylphosphinate; the polymer additive satisfies the double enthalpy ratio ΔH defined by the following formula (1): 0.90 ≤ ΔH ≤ 1.05; and satisfies 135°C ≤ T1 ≤ 160°C, 165°C ≤ T2 ≤ 185°C, 180°C ≤ T3 ≤ 200°C; Formula (1) ΔH = (H2 + H3) / H1. The polymer additive provided by the present invention has a specific crystal form transition state, and the polymer molding material added with the polymer additive has a lower molding shrinkage rate during the molding application process.

Description

Technical Field

[0001] The present invention belongs to the technical field of flame retardants, and more specifically, relates to polymer additives, flame retardants, polymer molding materials, and their preparation methods and applications. Background Art

[0002] Aluminum diethylphosphinate is a halogen-free and environmentally friendly flame retardant with a white powder appearance. It is insoluble in water and most organic solvents, and is easily soluble in strong acid and strong base solutions. It has the characteristics of high efficiency in flame retardancy, high thermal stability, low smoke, small particle size, small specific gravity, good dispersibility and compatibility. As a highly efficient and environmentally friendly halogen-free flame retardant, aluminum diethylphosphinate is widely used in the flame retardancy of thermoplastic plastics (such as PA6T, PA10T, PA66, PBT), fibers, and textiles.

[0003] The compounding system of aluminum diethylphosphinate is widely used in the field of halogen-free flame-retarded glass fiber reinforced engineering plastics. For example, the system of aluminum diethylphosphinate compounded with melamine polyphosphate (MPP), the system of aluminum diethylphosphinate compounded with melamine cyanurate (MCA), and the system of aluminum diethylphosphinate compounded with aluminum phosphite. These systems have the advantages of high flame retardancy efficiency, high temperature resistance, and small loss of resin matrix performance, so they are widely used.

[0004] During the application of aluminum diethylphosphinate in flame-retardant modification of thermoplastic plastics and other modified polymer composites, problems such as excessive molding shrinkage rate of the material often occur, resulting in problems such as the inability of injection-molded parts to match and install or combination looseness, which is particularly prominent in some fields of precision injection-molded parts.

[0005] Patent CN110407869A discloses a single aluminum trifluoropropylphosphinate flame retardant, which uses the compounding of single aluminum trifluoropropylphosphinate and aluminum diethylphosphinate to reduce the corrosion of the screw during the extrusion modification process of aluminum diethylphosphinate. However, it does not improve the problem of excessive molding shrinkage rate of the modified polymer composite. Patent CN113637193A discloses a nylon heat-insulating strip or reinforced nylon, glass fiber reinforced PA6 / PA66 composite material, including nylon 6633, aluminum diethylphosphinate, antioxidant, glass fiber, lubricant maleic anhydride grafted POE toughening agent and additive. By adding glass fiber to enhance the nylon itself, the water absorption rate of the composite material is reduced, and the molding shrinkage rate of the product becomes smaller, and the dimensional stability becomes better. However, in this scheme, aluminum diethylphosphinate is only used as a flame retardant component, and during its application process, aluminum diethylphosphinate will still cause the problem of excessive shrinkage rate during the molding of the modified polymer composite. Summary of the Invention

[0006] In view of the above existing technical problems, the primary object of the present invention is to provide a polymer additive, which has a relatively special crystal form and crystal structure, and has a lower molding shrinkage rate during the application of the polymer as an additive.

[0007] To achieve the above object, the present invention is realized through the following technical solutions:

[0008] The present invention claims protection for a polymer additive, comprising: aluminum diethylphosphinate and aluminum ethylbutylphosphinate;

[0009] The polymer additive satisfies the double enthalpy ratio ΔH defined by the following formula (1): 0.90 ≤ ΔH ≤ 1.05; and satisfies 135°C ≤ T1 ≤ 160°C, 165°C ≤ T2 ≤ 185°C, 180°C ≤ T3 ≤ 200°C;

[0010] Formula (1) ΔH = (H2 + H3) / H1;

[0011] The polymer additive is tested by differential scanning calorimetry (DSC), and the test method is as follows: under a nitrogen atmosphere, the polymer additive is heated from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min, held at this temperature for 3 minutes, and then cooled to room temperature at a rate of 20°C / min to obtain the cooling curve of the polymer additive; the above polymer additive is held at room temperature for 3 minutes, and then heated to a maximum temperature of 300°C again at a heating rate of 20°C / min to obtain the second heating curve of the polymer additive;

[0012] H1 is the peak area formed by the start temperature and end temperature of the exothermic peak on the cooling curve; two endothermic peaks on the second heating curve are selected, with the temperature increasing from low to high, H2 is the peak area formed by the start temperature and end temperature of the first endothermic peak on the second heating curve, and H3 is the peak area formed by the start temperature and end temperature of the second endothermic peak on the second heating curve.

[0013] T1 is the peak temperature of the exothermic peak on the cooling curve, T2 is the peak temperature of the first endothermic peak on the second heating curve, and T3 is the peak temperature of the second endothermic peak on the second heating curve.

[0014] Differential scanning calorimetry (DSC) is one of the most commonly used thermal analysis instruments. It can be used to characterize the melting and crystallization process of materials, reflecting the relationship between molecular chain structure and crystallization. In addition, for some substances without melting phenomenon, obvious endothermic peaks and exothermic peaks will appear during the DSC test. The difference between the endothermic peak and the exothermic peak is also related to the change of molecular structure or its crystallization performance. The change of molecular structure or its crystal structure directly determines the melting or crystallization behavior of DSC during heating or cooling, as well as the difference between the endothermic peak and the exothermic peak. The difference in molecular structure of materials will also affect their processing fluidity and mechanical properties during processing, and thus affect the dimensional stability and molding shrinkage of the material.

[0015] The present invention has found through research that although the polymer additive provided by the present invention has no melting phenomenon during the test process at 30-300°C, the endothermic peaks and exothermic peaks of different polymer additives are significantly different. The inventors have found through research that the specific double enthalpy ratio formed in the endothermic peak and the exothermic peak, as well as the specific peak temperature (T1, T2, T3), affect the specific crystallization transition state of the polymer additive. This state gives the polymer molding material better dimensional stability during the polymer molding process, so the polymer molding material exhibits a smaller molding shrinkage. The polymer molding material prepared by using the polymer additive having this specific crystal transition state as an additive has a lower molding shrinkage.

[0016] In some embodiments, the peak areas H1, H2, H3 and peak positions T1, T2, T3 can be obtained by peak marking and integral calculation of peak areas using existing methods in the art, such as peak marking and integral calculation of peak areas using software provided in the DSC device. Specifically, in some embodiments, when using differential scanning calorimetry DSC for testing, the weight of the test sample of the polymer additive can be 10±0.5 mg.

[0017] Specifically, in some embodiments, the peak areas H1, H2, H3 and the peak positions T1, T2, T3 can be integrated or marked multiple times and then averaged and tested, such as once, twice, three times, four times, five times, etc. More specifically, from the perspective of saving operations and maintaining data reproducibility and reliability, the peak areas H1, H2, H3 and the peak positions T1, T2, T3 can be tested 2-4 times and averaged and obtained.

[0018] In some embodiments, by weight percentage, the polymer additive comprises: 99.01 to 99.99% of aluminum diethylphosphinate and 0.01 to 0.99% of aluminum ethylbutylphosphinate. More specifically, the content of aluminum diethylphosphinate can be 99.10%, 99.20%, 99.30%, 99.40%, 99.50%, 99.60%, 99.70%, 99.80%, 99.90%, etc., or the range formed by any of the above values, such as 99.01 to 99.40%, 99.01 to 99.70%, 99.01 to 99.90%, 99.30 to 99.60%, 99.50 to 99.90%, 99.70 to 99.99%, 99.90 to 99.99%, etc., and the present invention is not limited thereto. More specifically, the content of aluminum ethylbutylphosphinate can be 0.03%, 0.05%, 0.08%, 0.10%, 0.20%, 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, 0.80%, 0.90%, 0.93%, 0.95%, 0.97%, etc., or the range formed by any of the above values, such as 0.01 to 0.10%, 0.01 to 0.30%, 0.01 to 0.70%, 0.10 to 0.80%, 0.30 to 0.90%, 0.70 to 0.93%, 0.80 to 0.99%, 0.90 to 0.99%, etc., and the present invention is not limited thereto.

[0019] In some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist in a physical combination form; in some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist in the form of ionic chemical coprecipitation of Formula I and Formula II; in some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist simultaneously in a physical combination form and in the form of ionic chemical coprecipitation of Formula I and Formula II.

[0020] 。

[0021] More specifically, in the present invention, the double enthalpy ratio ΔH can be 0.92, 0.94, 0.96, 0.98, 0.99, 1.00, 1.02, 1.04, 1.05, etc., or the range formed by any of the above values, such as 0.92 to 0.98, 0.96 to 1.05, etc., and the present invention is not limited thereto.

[0022] More specifically, in the present invention, the T1 can be 135°C, 138°C, 140°C, 142°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C, etc., or the range formed by any of the above values, such as 140°C to 150°C, 146°C to 154°C, etc., and the present invention is not limited thereto.

[0023] More specifically, in the present invention, the T2 can be 168°C, 170°C, 172°C, 174°C, 176°C, 178°C, 180°C, 183°C, etc., or an interval range formed by any of the above values, such as 174°C to 178°C, etc. The present invention is not limited thereto.

[0024] More specifically, in the present invention, the T3 can be 182°C, 184°C, 186°C, 188°C, 190°C, 192°C, 194°C, 196°C, 198°C, etc., or an interval range formed by any of the above values, such as 184°C to 188°C, 190°C to 192°C, etc. The present invention is not limited thereto.

[0025] In some embodiments, the polymer additive satisfies the double enthalpy ratio ΔH: 0.92 ≤ ΔH ≤ 1.05.

[0026] In some embodiments, the polymer additive satisfies 140°C ≤ T1 ≤ 156°C, 172°C ≤ T2 ≤ 178°C, 184°C ≤ T3 ≤ 192°C.

[0027] In some embodiments, the present invention claims a method for preparing a polymer additive, comprising the following steps:

[0028] S1. Under nitrogen protection, react a water-soluble salt or acid of hypophosphorous acid, an initiator with an olefin, adding 2.00 to 2.05 molecules of olefin relative to the P in each water-soluble salt or acid of hypophosphorous acid itself, to obtain an intermediate aqueous solution containing diethyl phosphinate;

[0029] S2. React the intermediate aqueous solution of step S1, a surfactant and an aluminum salt solution to obtain the polymer additive.

[0030] In the above embodiments, in step S1, the reaction temperature is 80 to 120°C.

[0031] In the above embodiments, in step S1, the reaction pressure is 0.6 to 2.0 MPa.

[0032] In the above embodiments, in step S1, heat preservation is carried out in two steps. For the first heat preservation, heat to 80 to 90°C, and the heat preservation time is 3.5 to 4.5 h. During the heat preservation process, the initiator is continuously added; then continue to heat preserve at 90 to 100°C for 0.5 to 1.5 h; or heat preservation is carried out in two steps. For the first heat preservation, heat to 105 to 115°C, and the heat preservation time is 3.5 to 4.5 h. During the heat preservation process, the initiator is continuously added; then continue to heat preserve at 105 to 115°C for 0.5 to 1.5 h.

[0033] In the above embodiments, in step S2, the mass concentration of diethyl phosphite in the intermediate aqueous solution is 15-25%; in step S2, the mass concentration of the water-soluble aluminum salt in the aluminum salt solution is 20-24%.

[0034] In the above embodiments, in step S2, the surfactant is selected from one or more of alkyl phosphate esters, alkyl phosphate salts, ether alcohol phosphate esters, and ether alcohol phosphate salts.

[0035] Specifically, the alkyl phosphate ester or alkyl phosphate salt may be selected from alkyl phosphate esters or alkyl phosphate salts having 8-18 carbon atoms; more specifically, the alkyl phosphate ester includes, but is not limited to, monolauric acid phosphate ester, etc.; the alkyl phosphate salt includes, but is not limited to, potassium monolauryl phosphate, etc. Specifically, the ether alcohol phosphate ester or ether alcohol phosphate salt may be selected from ether alcohol phosphate esters or ether alcohol phosphate salts having 8-18 carbon atoms; more specifically, the ether alcohol phosphate ester includes, but is not limited to, lauryl alcohol ether phosphate ester, etc.; the ether alcohol phosphate salt includes, but is not limited to, potassium lauryl phosphate, etc.

[0036] In the above embodiments, the addition amount of the surfactant is 0.001-0.10% of the weight of the intermediate aqueous solution. Further preferably, the addition amount of the surfactant is 0.01-0.08% of the weight of the intermediate aqueous solution.

[0037] In the above embodiments, before adding the surfactant, an alkali solution is further added to the intermediate aqueous solution for neutralization to remove the free acid in the solution system. More specifically, the neutralization is carried out until the pH is 5-6.5.

[0038] In the above embodiments, in step S2, the amounts of the intermediate aqueous solution and the aluminum salt solution are equal.

[0039] In the above embodiments, the aluminum salt solution is added at one time, and the temperature is raised to 50-60 °C during the addition of the aluminum salt solution, and the addition time is controlled to be 90-110 min; and / or

[0040] In step S2, the aluminum salt solution is added in two portions. The first portion is 15-35% equivalent of the aluminum salt solution, the addition time is controlled to be 30-40 min, and the temperature is controlled to be 35-45 °C; the second portion is 65-85% equivalent of the aluminum salt solution, the addition time is controlled to be 30-40 min, and the temperature is controlled to be 55-60 °C.

[0041] In some embodiments, the present invention claims another method for preparing a polymer additive, comprising the following preparation steps:

[0042] S1. Under nitrogen protection, react an aqueous hypophosphorous acid solution, an initiator with an olefin, adding 2.00 to 2.05 molecules of the olefin relative to P on the acid itself of each hypophosphorous acid, to obtain an intermediate aqueous solution containing diethylphosphinic acid;

[0043] S2. Prepare an aluminum hydroxide gel solution;

[0044] S3. Drop the intermediate aqueous solution from step S1 into the aluminum hydroxide gel solution from step S2 for reaction, heat up to 50 - 60 °C, and keep warm for 0.1 - 0.5 h; then heat up to 90 - 120 °C and keep warm for 0.5 - 5 h to obtain a polymer additive.

[0045] In the above - mentioned embodiment, in step S1, keep warm in two steps. The temperature for the first heat preservation is 75 - 85 °C, and the time is 2.5 - 3.5 h. During the heat preservation process, continuously supplement the initiator; during the heat preservation process, part of the reaction materials in the reactor are introduced into a Venturi ejector and fully mixed with the ethylene introduced into the Venturi ejector, and then enter the reactor after external circulation; then continue to keep warm for 0.5 - 1.5 h.

[0046] In the above - mentioned embodiment, in step S2, the reaction temperature for preparation is 10 - 20 °C.

[0047] In the above - mentioned embodiment, in step S3, heat up to 50 - 60 °C at a heating rate of 2 - 10 °C / h; and / or

[0048] In the above - mentioned embodiment, in step S3, heat up to 90 - 120 °C at a heating rate of 11 - 25 °C / h.

[0049] In the above - mentioned embodiment, in step S3, the molar ratio of diethylphosphinic acid to aluminum ions in the aluminum hydroxide gel solution is 3:1 - 1.01.

[0050] In some embodiments, the olefin can be at least one of ethylene, propylene, 1 - butene, 2 - butene, 1 - pentene, 1 - hexene or 1 - octene.

[0051] In some embodiments, the water - soluble salt of hypophosphorous acid can be potassium hypophosphite or sodium hypophosphite.

[0052] In some embodiments, the water - soluble aluminum salt can be an oxide, hydroxide, peroxide, sulfate, bisulfate, hydrated sulfate, persulfate, phosphate and / or phosphite of aluminum.

[0053] In some embodiments, the initiator is selected from one or more of organic peroxides, inorganic peroxides, and azo compounds. More specifically, the inorganic peroxide can be one or more of sodium persulfate, ammonium persulfate, or potassium persulfate. The organic peroxide can be one or more of benzoic acid peroxide, lauric acid peroxide, di-tert-butyl peroxide, percarbonate, acetic acid peroxide, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, or tert-butyl peroxypivalate; the azo compound can be one or more of azobisisobutyronitrile or azobisisoheptonitrile.

[0054] Furthermore, the present invention claims the use of the above polymer additive in reducing the shrinkage rate of polymers.

[0055] Furthermore, the present invention claims the use of the above polymer additive as a reactive and / or non-reactive flame retardant for polymers, as a flame retardant for varnishes and foamed coatings, as a flame retardant for wood and other cellulose-containing products, for preparing flame-retardant polymer molding materials, for preparing flame-retardant polymer molded articles, and / or for imparting flame retardancy to polyester and pure and blended cellulose fabrics by impregnation.

[0056] In some embodiments, the polymer additive is used together with a synergist; the synergist is melamine phosphate, bis(melamine) phosphate, penta(melamine) triphosphate, tris(melamine) diphosphate, tetra(melamine) triphosphate, hexa(melamine) pentaphosphate, diphosphomelamine, tetraphosphomelamine, pyrophosphomelamine, polyphosphomelamine, polyphosphoric acid melem, polyphosphoric acid melam, and / or polyphosphoric acid melon; is a melamine condensation product such as melem, melam, and / or melon; is a low polyester of tris(hydroxyethyl) isocyanurate / salt and aromatic polycarboxylic acid, benzoguanamine, tris(hydroxyethyl) isocyanurate / salt, allantoin, glycoluril, melamine, melamine cyanurate, cyanuric acid urea, dicyandiamide, and / or guanidine; is a nitrogen-containing phosphate of the formula (NH4) y H 3-y PO4 or (NH4PO3) z where y is 1 to 3 and z is 1 to 10,000; is aluminum phosphite, aluminum pyrophosphite; is zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, magnesium carbonate; is a salt of ethylphosphonic acid, a salt of butylphosphonic acid, a salt of n-butylphosphonic acid, a salt of sec-butylphosphonic acid, and / or a salt of hexylphosphonic acid.

[0057] In some embodiments, the polymer additive is used together with additives selected from at least one of antioxidants, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact modifiers, dyes or pigments.

[0058] In some embodiments, 0.0001 to 99.7999 wt% of the polymer additive, 0.1 to 40 wt% of the synergist and 0.1 to 40 wt% of the additive are used.

[0059] In some embodiments, the present invention claims a flame-retardant thermoplastic or thermosetting polymer molding material, polymer molded article, polymer film, polymer filament and / or polymer fiber, comprising: 0.5 to 45 wt% of the polymer additive, 0.5 to 95 wt% of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt% of a synergist and 0 to 55 wt% of a filler or reinforcing material.

[0060] In some embodiments, the polymer is selected from polyesters, polyamides, thermoplastic elastomers, thermoplastic polyurethanes, thermoplastic polyester elastomers, styrenic polymers, polyketones, polyolefins, polyacrylates and / or polymer blends containing polyamide or polyester.

[0061] In some embodiments, the polyolefin may be a polymer of monoolefins and diolefins such as polypropylene, polyisobutene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene or polybutadiene, and polymers of cycloolefins such as cyclopentene or norbornene; furthermore polyethylene (optionally crosslinkable), such as high density polyethylene (HDPE), high density and high molar mass polyethylene (HDPE-HMW), high density and ultra-high molar mass polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (VLDPE) and mixtures thereof.

[0062] The polyolefin can also be a copolymer of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene-1-butene copolymers, propylene-isobutene copolymers, ethylene-1-butene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and also terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene norbornene; furthermore mixtures of such copolymers with each other, such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer, LDPE / ethylene-acrylic acid copolymer, LLDPE / ethylene-vinyl acetate copolymer, LLDPE / ethylene-acrylic acid copolymer and alternating or statistically structured polyalkylene / carbon monoxide copolymers and their mixtures with other polymers such as polyamides.

[0063] In some embodiments, the styrenic polymers can be copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; high impact strength mixtures from styrene copolymers and another polymer such as polyacrylate, diene polymer or ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butene-styrene or styrene-ethylene / propylene-styrene.

[0064] In some embodiments, the styrenic polymer may be a graft copolymer of styrene or α-methylstyrene, such as styrene grafted on polybutadiene, styrene grafted on polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted on polybutadiene; styrene, acrylonitrile and methyl methacrylate grafted on polybutadiene; styrene and maleic anhydride grafted on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide grafted on polybutadiene; styrene and maleimide grafted on polybutadiene, styrene and alkyl acrylate or alkyl methacrylate grafted on polybutadiene, styrene and acrylonitrile grafted on ethylene-propylene-diene terpolymer, styrene and acrylonitrile grafted on polyalkyl acrylate or polymethyl alkyl acrylate, styrene and acrylonitrile grafted on acrylate-butadiene copolymer, and mixtures thereof, such as ABS polymer, MBS polymer, ASA polymer or AES polymer.

[0065] In some embodiments, the polyamide may be a polyamide and copolyamide derived from diamines and dicarboxylic acids and / or derived from aminocarboxylic acids or corresponding lactams, such as PA6, PA66, PA46, etc.; aromatic polyamides from m-xylene, diamines and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid and an elastomer optionally used as a modifier (polyhexamethylene isophthalamide, polyhexamethylene terephthalamide), such as poly-2,4,4-trimethylhexamethylene terephthalamide or polyphenylene isophthalamide; or a block copolymer of polyamide and polyolefin, olefin copolymer, ionomer or chemically bonded or grafted elastomer; or a block copolymer with a polyether, such as with polyethylene glycol, polypropylene glycol or polybutylene glycol.

[0066] In some embodiments, the polyester may be a polyester derived from dicarboxylic acids and diols and / or derived from hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dihydroxymethylcyclohexane terephthalate, polyhydroxybenzoate and block polyether esters derived from polyethers with hydroxy end groups; and polyesters modified with polycarbonate or MBS.

[0067] In some embodiments, the filler or reinforcing material may be an oxygen-containing compound of silicon, a magnesium compound, such as a metal carbonate of a metal in the second main group of the periodic table, magnesium oxide, magnesium hydroxide, hydrotalcite, dihydrotalcite, magnesium carbonate or magnesium calcium carbonate; calcium compounds such as calcium hydroxide, calcium oxide, hydrocalumite, aluminum compounds such as alumina, aluminum hydroxide, boehmite, diaspore or aluminum phosphate, red phosphorus, zinc compounds, glass fibers.

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] The present invention provides a polymer additive, the polymer additive having specific ΔH, T1, T2 and T3, the polymer additive within the above specific range having a specific crystal form transition state, and the polymer molding material added with the polymer additive having a lower molding shrinkage rate during the molding process. Detailed implementation mode

[0070] The present invention will be further described below in conjunction with the specification and specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

[0071] The raw materials used in the examples and comparative examples are described as follows:

[0072] Glass fiber, ECS10-03-568H, Jushi Co., Ltd.

[0073] Base resin 1: PA66, EPR24, Henan Shenma.

[0074] Base resin 2: PBT, GX121, Yizheng Chemical.

[0075] Base resin 3: PA6, M2000, Guangdong Xinhui Meida.

[0076] Synergist 1: melamine polyphosphate salt, MPP, Budit 3141, Budenheim.

[0077] Synergist 2: zinc borate, ZB-503, Anhui Yishitong Materials.

[0078] Synergist 3: aluminum phosphite, commercially available.

[0079] Sodium hypophosphite monohydrate, commercially available.

[0080] Sodium persulfate, commercially available.

[0081] Aluminum sulfate, commercially available.

[0082] Monolauryl phosphate, commercially available.

[0083] Lauryl alcohol ether phosphate, commercially available.

[0084] Potassium lauryl phosphate, commercially available.

[0085] Unless otherwise specified, the components selected in each parallel example and comparative example are the same commercially available products.

[0086] Example 1 A polymer additive

[0087] (1) Put 318 g of solid sodium hypophosphite monohydrate, 400 g of water, and 2 g of tert-butyl peroxy-2-ethylhexanoate into an autoclave. Replace the air in the reaction kettle with nitrogen 5 times. Then introduce ethylene into the autoclave. Keep the pressure of ethylene in the autoclave constant at 0.6 MPa through a pressure reducer. Heat it to 85 °C and keep it warm for 4 h. Continuously add 4 g of tert-butyl peroxy-2-ethylhexanoate during the 4 h of heat preservation. Then keep it warm at 95 °C for 1 h, cool it down and release the pressure to obtain an aqueous solution containing sodium diethylphosphinate.

[0088] (2) Add 20 wt% sodium hydroxide aqueous solution to the aqueous solution containing sodium diethylphosphinate obtained in step (1) to neutralize the free acid to pH = 6. Dilute it with water to make the mass concentration of sodium diethylphosphinate 20%. Add 0.03% (the addition amount is based on the weight of the diluted aqueous solution of sodium diethylphosphinate) of monolauryl phosphate. At 40 °C, slowly drip 1 / 6 equivalent (calculated based on the molar amount of sodium diethylphosphinate) of 20% aluminum sulfate aqueous solution, and the dripping time is 40 minutes. Raise the temperature to 55 °C and drip the remaining 5 / 6 equivalent (calculated based on the molar amount of sodium diethylphosphinate) of 20% aluminum sulfate aqueous solution, and the dripping time is 40 minutes. Then carry out cooling and filtration in turn. Wash the filter cake 3 times with water 3 times the weight of the filter cake, and then dry it at 120 °C to constant weight to obtain a polymer additive.

[0089] Example 2 A polymer additive

[0090] (1) Put 318 g of solid sodium hypophosphite monohydrate, 400 g of water, and 2 g of sodium persulfate into an autoclave. Replace the air in the autoclave with nitrogen 5 times. Then introduce ethylene into the autoclave. Keep the pressure of ethylene in the autoclave constant at 1.5 MPa through a pressure reducer. Heat it to 110 °C and keep it warm for 4 h. Continuously add the solution prepared by dissolving 4 g of sodium persulfate and 36 g of water during the 4 h of heat preservation. Then keep it warm at 110 °C for 1 h, cool it down and release the pressure to obtain an aqueous solution containing sodium diethylphosphinate.

[0091] (2) Add 20 wt% sodium hydroxide aqueous solution to the aqueous solution containing sodium diethylphosphinate obtained in step (1) to neutralize the free acid to pH = 6. Dilute it with water to make the mass concentration of sodium diethylphosphinate 20%. Add 0.02% (the addition amount is based on the weight of the diluted aqueous solution of sodium diethylphosphinate) of lauryl ether alcohol phosphate. At 35 °C, slowly drip 1 / 6 equivalent (calculated based on the molar amount of sodium diethylphosphinate) of 20% aluminum sulfate aqueous solution, and the dripping time is 40 minutes. Raise the temperature to 55 °C and drip the remaining 5 / 6 equivalent (calculated based on the molar amount of sodium diethylphosphinate) of 20% aluminum sulfate aqueous solution, and the dripping time is 30 minutes. Then carry out cooling and filtration in turn. Wash the filter cake 3 times with water 3 times the weight of the filter cake, and then dry it at 120 °C to constant weight to obtain a polymer additive.

[0092] Example 3 A polymer additive

[0093] The difference between this example and Example 1 is as follows:

[0094] (2) The aqueous solution containing sodium diethylphosphinate obtained in step (1) is added with a 20 wt% aqueous sodium hydroxide solution to neutralize the free acid to pH = 6, diluted with water to a mass concentration of sodium diethylphosphinate of 20%, 0.04% (the addition amount is based on the weight of the diluted aqueous sodium diethylphosphinate solution) of lauryl ether alcohol phosphate is added, and an aqueous solution of aluminum sulfate with a mass concentration of 20% and 1 / 3 equivalent (calculated based on the molar amount of sodium diethylphosphinate) is added dropwise at 35°C, and the dropping time is 40 minutes; the temperature is raised to 55°C, and the remaining 2 / 3 equivalent (calculated based on the molar amount of sodium diethylphosphinate) of the aqueous solution of aluminum sulfate with a mass concentration of 20% is added dropwise, and the dropping time is 20 minutes; then cooling and filtration are carried out in sequence, the filter cake is washed 3 times with water 3 times the weight of the filter cake, and then dried at 120°C to constant weight to obtain the polymer additive.

[0095] Example 4 A polymer additive

[0096] The difference between this example and Example 2 is as follows:

[0097] (2) The aqueous solution containing sodium diethylphosphinate obtained in step (1) is added with a 20 wt% aqueous sodium hydroxide solution to neutralize the free acid to pH = 6, diluted with water to a mass concentration of sodium diethylphosphinate of 22%, 0.05% (the addition amount is based on the weight of the diluted aqueous sodium diethylphosphinate solution) of potassium lauryl phosphate is added, and an aqueous solution of aluminum sulfate with a mass concentration of 22% and 1 equivalent (calculated based on the molar amount of sodium diethylphosphinate) is added dropwise at 30°C, and at the same time, the temperature is slowly raised to 60°C at a heating rate of 4°C / 10 minutes, and the total dropping time is 100 minutes; then cooling and filtration are carried out in sequence, the filter cake is washed 3 times with water 3 times the weight of the filter cake, and then dried at 120°C to constant weight to obtain the polymer additive.

[0098] Example 5 A polymer additive

[0099] (1) Charge 396 kg of an aqueous solution of hypophosphorous acid with a mass content of 50% into an autoclave. Replace the air in the autoclave with nitrogen at 0.6 MPa for 5 times. Charge ethylene into the autoclave until the ethylene pressure in the autoclave reaches 1.0 MPa. Stir and heat to 80 °C, keep warm for 3 h, and continuously add 40 g of an aqueous solution of sodium persulfate with a mass content of 10% during the 2-h insulation period. During the insulation process, the material is pumped from the bottom valve of the autoclave through a centrifugal pump into the liquid inlet of the Venturi injector, and the upper-layer ethylene gas in the reaction kettle enters from the gas inlet of the Venturi injector. The gas-liquid two-phase is fully mixed and enters the reaction kettle through external circulation. Ethylene enters from the gas inlet of the Venturi injector to supplement the consumed ethylene to maintain the reaction kettle pressure stable at 1.0 MPa. After the initiator addition is completed, keep warm for 1 h, cool and vent to obtain an aqueous solution containing diethylphosphinic acid.

[0100] (2) At 20 °C, prepare an aqueous sodium hydroxide solution with 60 g of sodium hydroxide and 1140 g of water. Slowly drip the aqueous sodium hydroxide solution into an aqueous aluminum sulfate solution prepared with 333 g of aluminum sulfate octadecahydrate and 777 g of water within 1.5 h to obtain an aluminum hydroxide gel solution.

[0101] (3) Continuously drip the aluminum hydroxide gel solution into the aqueous solution containing diethylphosphinic acid (the molar ratio of diethylphosphinic acid to aluminum ions is 3:1) within 3 h. Then, increase the temperature at a rate of 5 °C / h to 60 °C, keep warm for 0.5 h, then increase the temperature at a rate of 20 °C / h to 100 °C, keep warm for 0.5 h, and then cool and filter in sequence. The filter cake is washed 3 times with water three times the weight of the filter cake, and then dried at 120 °C to constant weight to obtain a polymer additive.

[0102] Example 6 A polymer additive

[0103] The difference between this example and Example 5 is as follows:

[0104] (2) At 10 °C, prepare an aqueous sodium hydroxide solution with 60 g of sodium hydroxide and 1140 g of water. Slowly drip the aqueous sodium hydroxide solution into an aqueous aluminum sulfate solution prepared with 333 g of aluminum sulfate octadecahydrate and 777 g of water within 1.5 h to obtain an aluminum hydroxide gel solution.

[0105] (3) Continuously drip the aluminum hydroxide gel solution into the aqueous solution containing diethylphosphinic acid (the molar ratio of diethylphosphinic acid to aluminum ions is 3:1) within 3 h. Then, increase the temperature at a rate of 10 °C / h to 60 °C, keep warm for 0.5 h, then increase the temperature at a rate of 20 °C / h to 100 °C, keep warm for 0.5 h, and then cool and filter in sequence. The filter cake is washed 3 times with water three times the weight of the filter cake, and then dried at 120 °C to constant weight to obtain a polymer additive.

[0106] Comparative Example 1

[0107] Use the existing polymer additive 1, XHPFR-1040, Zhejiang Xinhuachem Co., Ltd.

[0108] Comparative Example 2

[0109] Use the existing polymer additive 2, ADP-30, Lanzhou Ruipu Technology Co., Ltd.

[0110] Test Example

[0111] (1) Dissolve the polymer additives obtained in Examples 1-6 and the polymer additives of Comparative Examples 1-2 in deuterated aqueous sodium hydroxide solution, and test their nuclear magnetic phosphorus spectra.

[0112] (1) Instrument: Nuclear magnetic resonance spectrometer (Bruker 400M).

[0113] (2) Reagent: 10wt% deuterated aqueous sodium hydroxide solution.

[0114] (3) Experimental method: Weigh about 0.1 g (accurate to 0.0001 g) of the sample to be tested, add 5 g of deuterated aqueous sodium hydroxide solution, and dissolve it by ultrasonic wave; transfer it to a nuclear magnetic tube, then place the nuclear magnetic tube in a nuclear magnetic resonance analyzer, scan it, obtain the nuclear magnetic resonance spectrum, integrate aluminum diethylphosphinate and aluminum ethylbutylphosphinate in the nuclear magnetic resonance spectrum, obtain their molar percentages, and after conversion, obtain their mass percentages.

[0115] The test results of the polymer additives are shown in Table 1 below in terms of mass percentage.

[0116] Table 1

[0117]

[0118] (2) Use differential scanning calorimetry (DSC 214, NETZSCH DSC 204 F1, Germany) to test the polymer additives obtained in Examples 1-6 and the polymer additives of Comparative Examples 1-2. The test method is as follows: Under a nitrogen atmosphere, the polymer additive is heated from room temperature to a maximum temperature of 300 °C at a heating rate of 20 °C / min, held at this temperature for 3 min, and then cooled to room temperature at a rate of 20 °C / min to obtain the cooling curve of the polymer additive; after the above polymer additive is held at room temperature for 3 min, it is heated to a maximum temperature of 300 °C again at a heating rate of 20 °C / min to obtain the second heating curve of the polymer additive.

[0119] Among them, H1 is the peak area formed by the starting temperature and the ending temperature of the exothermic peak in the cooling curve; two endothermic peaks on the second heating curve are selected, with the temperature increasing from low to high. H2 is the peak area formed by the starting temperature and the ending temperature of the first endothermic peak on the second heating curve, and H3 is the peak area formed by the starting temperature and the ending temperature of the second endothermic peak on the second heating curve;

[0120] In Table 2 below, ΔH = (H2 + H3) / H1;

[0121] T1 is the peak temperature of the exothermic peak in the cooling curve, T2 is the peak temperature of the first endothermic peak on the second heating curve, and T3 is the peak temperature of the second endothermic peak on the second heating curve.

[0122] The above peak temperatures and peak areas are calibrated or calculated through the software built in NETZSCH DSC 204 F1.

[0123] The test data of the polymer additives in Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 2 below.

[0124] Table 2

[0125]

[0126] (3) The polymer additives in Examples 1 to 6 and Comparative Examples 1 to 2 are used as flame retardants and are melt - blended and extruded with a synergist, glass fiber, and a base resin to obtain polymer molding materials. By weight, the amounts of each component in Examples 7 to 16 and Comparative Examples 3 to 5 are shown in Table 3.

[0127] Table 3

[0128]

[0129] The molding shrinkage rates of the polymer molding materials prepared in Examples 7 to 16 and Comparative Examples 3 to 5 are tested. The test method is carried out in accordance with GB / T 15585 - 1995 to measure the shrinkage rate after 48 h. The test results are shown in Table 4 below.

[0130] Table 4

[0131]

[0132] From the data of the examples, it can be seen that the polymer molding materials added with polymer additives have lower molding shrinkage rates during the molding process. The transverse shrinkage rate of the polymer molding materials added with polymer additives is ≤0.81%, and the longitudinal molding shrinkage rate is ≤0.29%.

[0133] As can be seen from Example 7, Example 13, and Example 14, good molding shrinkage rates can be achieved by using different synergistic agents in the polymer molding material. As can be seen from Example 7, Example 15, and Example 16, good molding shrinkage rates can be achieved by using different base resins to prepare the polymer molding material.

[0134] As can be seen from the examples, Comparative Example 3, and Comparative Example 4, when the double enthalpy ratio ΔH of the polymer additive, as well as T1, T2, and T3 are within a specific range, the transverse shrinkage rate and the longitudinal shrinkage rate of the polymer molding material added with the polymer additive both decrease significantly.

[0135] The foregoing examples are merely illustrative and are used to explain some features of the method of the present invention. The appended claims are intended to claim the broadest scope conceivable, and the examples presented herein are supported by the applicant's actual test results. Therefore, the applicant's intention is that the appended claims not be limited by the selection of examples that illustrate the features of the present invention. Some of the numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be interpreted as being covered by the appended claims whenever possible.

Claims

1. A polymer additive, characterized in that, Comprising: Aluminum diethylphosphinate and aluminum ethylbutylphosphinate; The polymer additive satisfies the double enthalpy ratio ΔH defined by the following formula (1): 0.90 ≤ ΔH ≤ 1.05; and satisfies 135°C ≤ T1 ≤ 160°C, 165°C ≤ T2 ≤ 185°C, 180°C ≤ T3 ≤ 200°C; Formula (1) ΔH = (H2 + H3) / H1; The polymer additive is tested by differential scanning calorimetry (DSC). The test method is as follows: Under a nitrogen atmosphere, the polymer additive is heated from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min, held at this temperature for 3 min, and then cooled to room temperature at a rate of 20°C / min to obtain the cooling curve of the polymer additive; The above polymer additive is held at room temperature for 3 min, and then heated again to a maximum temperature of 300°C at a heating rate of 20°C / min to obtain the second heating curve of the polymer additive; H1 is the peak area formed by the start temperature and end temperature of the exothermic peak on the cooling curve; Select two endothermic peaks on the second heating curve, from low to high temperature. H2 is the peak area formed by the start temperature and end temperature of the first endothermic peak on the second heating curve, and H3 is the peak area formed by the start temperature and end temperature of the second endothermic peak on the second heating curve; T1 is the peak temperature of the exothermic peak on the cooling curve, T2 is the peak temperature of the first endothermic peak on the second heating curve, and T3 is the peak temperature of the second endothermic peak on the second heating curve.

2. The polymer additive according to claim 1, characterized in that, By weight percentage, the polymer additive comprises: 99.01 - 99.99% of aluminum diethylphosphinate and 0.01 - 0.99% of aluminum ethylbutylphosphinate.

3. The polymer additive according to claim 1, wherein Aluminum diethylphosphinate and aluminum ethylbutylphosphinate exist in the form of ionic chemical coprecipitation, or in the form of physical combination and ionic chemical coprecipitation; The form of ionic chemical coprecipitation exists in the form of ionic chemical coprecipitation of formula I and formula II; 。 4. The polymer additive according to claim 1, wherein The polymer additive satisfies the double enthalpy ratio ΔH: 0.92 ≤ ΔH ≤ 1.

05.

5. The polymer additive according to claim 1 or 4, characterized in that, The polymer additive satisfies 140°C ≤ T1 ≤ 156°C, 172°C ≤ T2 ≤ 178°C, 184°C ≤ T3 ≤ 192°C.

6. The preparation method of the polymer additive according to any one of claims 1 to 5, characterized in that, Including the following steps: S1. Under nitrogen protection, a water-soluble salt or acid of hypophosphorous acid, an initiator and an olefin are reacted. 2.00 to 2.05 molecules of olefin are added per P in the water-soluble salt or acid of hypophosphorous acid itself to obtain an intermediate aqueous solution containing aluminum diethylphosphinate; S2. The intermediate aqueous solution in step S1, a surfactant and an aluminum salt solution are reacted to obtain the polymer additive.

7. The preparation method according to claim 6, characterized in that, In step S1, the reaction temperature is 80 - 120°C.

8. The preparation method according to claim 6, wherein In step S1, the reaction pressure is 0.6 - 2.0 MPa.

9. The preparation method according to claim 6, wherein In step S2, the mass concentration of aluminum diethylphosphinate in the intermediate aqueous solution is 15 - 25%; In step S2, the mass concentration of the water-soluble aluminum salt in the aluminum salt solution is 20 - 24%.

10. The preparation method according to claim 6, characterized in that, In the step S2, the surfactant is selected from one or more of alkyl phosphate esters, alkyl phosphate salts, ether alcohol phosphate esters, and ether alcohol phosphate salts.

11. The preparation method according to claim 6, characterized in that: In step S2, the aluminum salt solution is added at one time, the temperature is raised to 50-60° C. during the addition process, and the addition time is controlled to be 90-110 min; or In step S2, aluminum salt solution is added twice. The first time, 15-35% equivalent aluminum salt solution is added, the addition time is controlled to be 30-40 minutes, and the temperature is controlled to be 35-45°C; the second time, 65-85% equivalent aluminum salt solution is added, the addition time is controlled to be 30-40 minutes, and the temperature is controlled to be 55-60°C.

12. The preparation method of the polymer additive according to any one of claims 1 to 5, characterized in that, The method comprises the following preparation steps: S1. Under nitrogen protection, an aqueous solution of hypophosphorous acid, an initiator and an olefin are reacted, and 2.00 to 2.05 molecules of olefin are added relative to the P of each hypophosphorous acid itself to obtain an aqueous intermediate solution containing diethylphosphinic acid; S2. Preparing an aluminum hydroxide gel solution; S3. The intermediate aqueous solution of step S1 is added dropwise to the aluminum hydroxide gel solution of step S2 for reaction, and the temperature is raised to 50-60°C and kept for 0.1-0.5h; the temperature is then raised to 90-120°C and kept for 0.5-5h to obtain a polymer additive.

13. Use of the polymer additive according to any one of claims 1 to 5 for reducing the shrinkage of a polymer.

14. Use of the polymer additive according to any one of claims 1 to 5 as a reactive and / or non-reactive flame retardant for polymers, as a flame retardant for varnishes and foaming coatings, as a flame retardant for wood and other cellulose-containing products, for the preparation of flame-retardant polymer molding materials, for the preparation of flame-retardant polymer moldings and / or for imparting flame retardancy to polyester and pure and blended cellulose fabrics by impregnation.

15. The use according to claim 14, wherein, The polymer additive is used together with a synergist; the synergist is melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine, and / or melamine cyanurate; and is a nitrogen-containing phosphate of the formula (NH4) y H 3-y PO4 or (NH4PO3) z , where y is from 1 to 3 and z is from 1 to 10,000; is aluminum phosphite, aluminum pyrophosphite; is zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, magnesium carbonate; is a salt of ethylphosphonic acid, a salt of butylphosphonic acid, a salt of n-butylphosphonic acid, a salt of sec-butylphosphonic acid, and / or a salt of hexylphosphonic acid.

16. The use according to claim 14, characterized in that, The polymer additive is used together with an additive selected from at least one of antioxidants, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact modifiers, dyes or pigments.

17. The use according to claim 16, characterized in that, 0.0001-99.7999 wt% of the polymer additive, 0.1-40 wt% of the synergist and 0.1-40 wt% of the additive are used.

18. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer molded articles, polymer films, polymer filaments, and / or polymer fibers, characterized in that, The invention comprises: 0.5 to 45 wt % of the polymer additive according to any one of claims 1 to 5, 0.5 to 95 wt % of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt % of a synergist and 0 to 55 wt % of a filler or a reinforcing material.

19. The flame-retardant thermoplastic or thermosetting polymer molding material, polymer molded body, polymer film, polymer filament and / or polymer fiber according to claim 18, characterized in that, The polymer is selected from polyesters, polyamides, thermoplastic elastomers, styrenic polymers, polyketones, polyolefins, polyacrylates and / or polymer blends comprising polyamides or polyesters.

20. The flame-retardant thermoplastic or thermosetting polymer molding material, polymer molded article, polymer film, polymer filament and / or polymer fiber according to claim 19, characterized in that, The thermoplastic elastomer is a thermoplastic polyester elastomer.

21. The flame-retardant thermoplastic or thermosetting polymer molding material, polymer molded body, polymer film, polymer filament and / or polymer fiber according to claim 19, characterized in that, The thermoplastic elastomer is thermoplastic polyurethane.

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