CN104312093A - Halogen-free flame-retardant PBT/PP (polybutylece terephthalate/propylene)-based wood plastic composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant PBT/PP (polybutylece terephthalate/propylene)-based wood plastic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of wood plastic composite materials and particularly relates to a halogen-free flame-retardant PBT/PP (polybutylece terephthalate/propylene)-based wood plastic composite material and a preparation method thereof. The wood plastic composite material is prepared from the following raw materials in parts by weight: 20-30 parts of polybutylene terephthalate, 10-20 parts of propylene, 28-35 parts of melamino-formaldehyde modified plant fibers, 18-23 parts of coated ammonium polyphosphate, 1-3 parts of a 4A molecular sieve, 4-8 parts of maleic anhydride grafted polyolefin, 2-3 parts of a lubricant, 0.2-0.5 part of an antioxidant and 0.2-0.5 part of a light stabilizer. The wood plastic composite material provided by the invention is high in mechanical strength, and vertical combustion of a sample bar which is 1.6mm thick passes UL-94V-0 grade, the tensile strength reaches 36.3MPa, the bending strength reaches 48.8MPa, the thermal deformation temperature is 144.8 DEG C, and the long-term using temperature reaches up to 120 DEG C.
Description
Technical field
The present invention relates to wood plastic composite technical field, be specifically related to a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material and preparation method thereof.
Background technology
Vegetable fibre as wood powder, bamboo powder have that specific tenacity is high, specific surface area is large, density is low, the advantage such as little and renewable and biodegradable to equipment attrition, suitably rear and thermoplastics compound are processed to it, the environmental protection wood plastic composite of high-performance, high added value can be obtained.The vegetable fibre heat decomposition temperatures such as wood powder, bamboo powder are lower, generally just start to decompose at 150 ~ 200 DEG C, mostly adopt the thermoplasticity general-purpose plastics that processing temperature is lower as the compound with it such as polyethylene, polypropylene (PP), polyvinyl chloride at present, but there is the shortcomings such as mechanical strength is lower, thermotolerance is poor in gained wood plastic composite.Thermoplastics matrix is larger on composite property impact, polybutylene terephthalate (PBT) is a kind of thermoplastic semi-crystalline's type resin, compared to polyethylene, polypropylene, polyvinyl chloride etc., there is higher mechanical strength, thermotolerance, over-all properties is more excellent, be widely used in the fields such as electric, automotive industry, machinery instrument, signal equipment and lamp component, its reclaimed materials has higher utility value.PBT is polar polymer, plant fibre surface contains a large amount of hydroxyls, there is higher surface energy and wetting ability, both consistencies are better, but the fusing point of PBT is 225 ~ 235 DEG C, processing melt temperature reaches 235 ~ 250 DEG C, easily there is thermolysis in vegetable fibre under so high processing temperature, and degradation production also can cause PBT to degrade, both simple blend gained composite properties are poor like this, are therefore the development and utilization that the wood plastic composite of matrix is not applied for a long time with PBT.Carry out modification to vegetable fibre, make it have higher thermostability at about 200 DEG C, reduce the PBT palliating degradation degree that thermolysis under processing temperature and degradation production cause, being expected to obtain high performance take PBT as the wood plastic composite of matrix.
In addition, the fire-retardant particularly halogen-free flameproof of wood plastic composite is also significant problem in the urgent need to address in its application process.The halogen-free flameproof of existing wood plastic composite is mainly based on ammonium polyphosphate (APP), the patent No. is that the Chinese invention patent of ZL200710173607.X discloses a kind of halogen-free flameproof cellulosic material composition, said composition is made up of cellulosic material, water-soluble poly ammonium phosphate and watersoluble melamine, can be used as the halogen-free expanded flame-retardant agent in wood plastic composite, extender and/or toughener.The patent No. is that the Chinese invention patent of ZL201210097608.1 discloses a kind of Anti-mildew halogen-free flame-retardant smoke-suppression wood-plastic composite material, and this patent adopts the polyvinyl chloride (PVC) of difficult combustion and magnesium hydroxide etc. to reduce the usage quantity of main ammonium polyphosphate flame retardant.Above two patents are directly fire retardant with ammonium polyphosphate, and because ammonium polyphosphate is inorganics, resistance to water-soluble poor with resistance to water soak, with organic polymer matrix poor compatibility, obtained flame-retardant composite property is poor.The patent No. is that the Chinese invention patent of ZL201010179160.9 discloses a kind of halogen-free flame-retardant type injection molding-class polyolefin wood plastic matrix material and preparation method thereof, the method adopts red phosphorus and the composite flame-proof such as magnesium hydroxide, borax, amount of flame-retardant agent is less, halogen-free flameproof is effective, but the intrinsic redness of red phosphorus limits its use range.
PBT easy firing, and discharge a large amount of heat during burning, be that the wood plastic composite of matrix also needs halogen-free flameproof modification with PBT.Melamine phosphate, phosphinates etc. have good fire retardation to PBT, the patent No. is the preparation method that the Chinese invention patent of ZL200810089638.1 discloses a kind of high machinery performance halogen-free anti-flaming PBT composite, and the method adopts melamine phosphate and the phosphinates compositional flame-retardant through pyroprocessing; The patent No. is that the Chinese invention patent of ZL201210410982.2 discloses a kind of fire-retardant chain extension polybutylene terephthalate composition and method of making the same, this patent adopts aluminum diethylphosphinate and the side composite PBT of the making flame retardant properties of base band epoxy group(ing) polysiloxane to reach UL94V-0@1.6mm, fire retardation is better, but the equal price of flame-retardant system used is high, fire-retardant cost is very high.
In sum, existing wood plastic composite adopts the general-purpose plastics such as polyethylene, polypropylene, polyvinyl chloride to be matrix substantially, there is mechanical strength low, poor heat resistance, and be the serious deterioration such as mechanical property, resistance toheat after fire retardant halogen-free flameproof with ammonium polyphosphate, and with PBT engineering plastics for matrix, because the vegetable fibre such as wood powder, bamboo powder under processing temperature decomposes, be also difficult to obtain high performance wood plastic composite.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, this wood plastic composite has excellent fireproof performance, good mechanical properties, life-time service temperature high.
Another object of the present invention is to the preparation method providing a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, this preparation method's technique is simple, and convenient operation and control, steady quality, production efficiency is high, can large-scale industrial production.
Object of the present invention is achieved through the following technical solutions: a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, is characterized in that: described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 20-30 part, polypropylene 10-20 part, terpolycyantoamino-formaldehyde resin modified plant fibers 28-35 part, cladded type ammonium polyphosphate 18-23 part, 4A molecular sieve 1-3 part, maleic anhydride stem grafting polyolefin 4-8 part, lubricant 2-3 part, oxidation inhibitor 0.2-0.5 part and photostabilizer 0.2-0.5 part.
Preferably, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 22-28 part, polypropylene 12-18 part, terpolycyantoamino-formaldehyde resin modified plant fibers 29-33 part, cladded type ammonium polyphosphate 19-21 part, 4A molecular sieve 1.5-2.5 part, maleic anhydride stem grafting polyolefin 5-7 part, lubricant 2.2-2.8 part, oxidation inhibitor 0.2-0.4 part and photostabilizer 0.2-0.4 part.
More preferred, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 25 parts, polypropylene 15 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 31 parts, cladded type ammonium polyphosphate 20 parts, 2 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 6 parts, lubricant 2.5 parts, 0.3 part, oxidation inhibitor and photostabilizer 0.3 part.
Preferably, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified wood powder or terpolycyantoamino-formaldehyde resin modified bamboo powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 40-100 object wood powder or bamboo powder, add 10-15L deionized water, after stirring 10-15min, add 0.15-0.20kg zinc borate or boric acid, continue to stir 45-60min;
(2) in another reactor, add 2.1-2.4kg trimeric cyanamide and 3.5-4.5L massfraction is the formalin of 35-39%, with glacial acetic acid, pH is transferred to 4.5-5.5, at 70-80 DEG C of temperature, heats 30-45min, obtained trimeric cyanamide methylol performed polymer;
(3) getting the obtained trimeric cyanamide methylol performed polymer of 5-7L step (2) is poured in the obtained system of step (1), be warmed up to 60-70 DEG C, after stirring l-2h, with the aqueous sodium carbonate that massfraction is 4-6%, pH value is transferred to 6.5-7.5, filters after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 3-4h at 80-85 DEG C of temperature, then at 105-110 DEG C of temperature dry 4-6h, obtained terpolycyantoamino-formaldehyde resin modified wood powder or terpolycyantoamino-formaldehyde resin modified bamboo powder.
Preferably, described cladded type ammonium polyphosphate is silane cladded type ammonium polyphosphate or melamine resin cladded type ammonium polyphosphate, and the particle diameter of cladded type ammonium polyphosphate is 10-20 μm, and the polymerization degree is 1000-5000, and phosphorus is containing amount≤28%, and nitrogen is containing amount≤14%.
Preferably, described maleic anhydride stem grafting polyolefin is maleic anhydride inoculated polypropylene and/or maleic anhydride graft high density polyethylene(HDPE), and the percentage of grafting of maleic anhydride stem grafting polyolefin is more than or equal to 5%.
Preferably, described lubricant is at least one in dimethyl silicone oil, methyl phenyl silicone oil, polyethylene wax, stearic acid and stearate soap; Described stearate soap is at least one in calcium stearate, Magnesium Stearate and sodium stearate.
Preferably, described oxidation inhibitor is phenolic antioxidant and/or phosphite ester kind antioxidant; Described phenolic antioxidant is antioxidant 1010 and/or antioxidant 1076; Described phosphite ester kind antioxidant is irgasfos 168 and/or oxidation inhibitor 626.
The chemical name of antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; The chemical name of antioxidant 1076 is β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid; The chemical name of irgasfos 168 is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester; The chemical name of oxidation inhibitor 626 is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
More preferred, the mixture that described oxidation inhibitor is made up of with weight ratio 1:1 or 1:2 antioxidant 1010 and irgasfos 168.
Preferably, described photostabilizer is at least one in photostabilizer GW-770, ultraviolet absorbent UV-531, UV light absorber UV-329, photostabilizer GW-540, ultraviolet absorbent uv-326, photostabilizer GW-622 and photostabilizer GW-944.
The chemical name of photostabilizer GW-770 is two (2,2,6,6-tetramethyl-piperidyl) sebates; The chemical name of ultraviolet absorbent UV-531 is 2 – Qiang Ji – 4 – oxy-octyl benzophenones; The chemical name of UV light absorber UV-329 is the special octyl phenyl of 2-(2'-hydroxyl-5'-) benzotriazole; The chemical name of photostabilizer GW-540 is three (1,2,2,6,6-pentamethvl base) phosphorous acid ester; The chemical name of ultraviolet absorbent uv-326 is 2-(2 ＇-hydroxyl-3 ＇-tertiary butyl-5 ＇-aminomethyl phenyl)-5-chlorinated benzotriazole; The chemical name of photostabilizer GW-622 is poly-[1-(2`-hydroxyethyl)-2,2,6,6-tetramethyl--4-hydroxy piperidine succinic acid fat]; The chemical name of photostabilizer GW-944 is poly-{ [6-[(1,1,3,3 ,-tetramethyl butyl)-amido] 1,3,5 ,-triazine-2,4-bis-base] [(2,2,6,6-tetramethyl-piperidyl)-imido grpup]-1,6-hexane two base-[(2,2,6,6-tetramethyl-piperidyl)-imido grpup].
Another object of the present invention is achieved through the following technical solutions: the preparation method of a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 180-200 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
Preferably, the whipping temp of described high speed blender is 80-120 DEG C, and churning time is 5-10min; The extruder temperature of described twin screw extruder is: a district temperature 195-200 DEG C, two district temperature 195-200 DEG C, three district temperature 190-195 DEG C, four district temperature 185-190 DEG CHe five district temperature 180-185 DEG C; The rate of feeding of twin screw extruder is 23-27r/min, and engine speed is 70-100r/min.
Beneficial effect of the present invention is: fire retardant PBT with no halogen of the present invention/PP base wood-plastic composite material with the PBT/PP of certain proportioning for matrix, with this, system melt temperature is down to less than 200 DEG C, the mechanical strength of PBT engineering plastics and higher heat-drawn wire can be kept largely again; The present invention adopts terpolycyantoamino-formaldehyde resin to carry out coated to vegetable fibre, improves its thermostability, and strengthens the expandable flame retardant effect with cladded type ammonium polyphosphate; The present invention adopts cladded type ammonium polyphosphate good flame retardation effect, and can improve material resistance to water-soluble, resistance to water soak, powder processing fluidity and dispersiveness, with the consistency of matrix and the performance such as cementability, anti-precipitation ability; The present invention adopts 4A molecular sieve to absorb a small amount of moisture content that in the course of processing, wood powder decomposition produces, and reduces the hydrolytic deterioration to PBT, and stablizes foamed char, reach the effect of fire-retardant synergistic; The present invention adopts maleic anhydride stem grafting polyolefin increase-volume, can obtain halogen-free flameproof and the high wood plastic composite of tensile strength, flexural strength and use temperature.
Fire retardant PBT with no halogen of the present invention/PP base wood-plastic composite material adopts cladded type ammonium polyphosphate as expanding halide-free fire-retardant, add 4A molecular sieve again as fire retarding synergist, make 1.6mm batten vertical combustion test by UL94V-0 level, limiting oxygen index(LOI) more than 29%, excellent fireproof performance; And the tensile strength of wood plastic composite reaches 36.3MPa, flexural strength reaches 48.8MPa, good mechanical properties, and heat-drawn wire reaches 144.8 DEG C, and life-time service temperature is high.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, can large-scale industrial production.
Embodiment
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
The polybutylene terephthalate that following embodiment adopts is purchased from Changchun chemical industry (Jiangsu) company limited product, and the trade mark is 1100-211M; Polypropylene is purchased from Beijing Yanshan Petrochemical Company, and the trade mark is K2035, and melt flow rate (MFR) is 35g/10min; Maleic anhydride inoculated polypropylene is purchased from the serial trade mark product of Ningbo NengZhiGuang New Materials Science Co., Ltd, and the trade mark is GPM200A(melt flow rate (MFR) is 160g/10min), GPM200AL(melt flow rate (MFR) is 30g/10min) and GPM200B(melt flow rate (MFR) be 25g/10min); Maleic anhydride graft high density polyethylene(HDPE) is purchased from sea, Hangzhou one macromolecular material company limited, and the trade mark is EPA830H, and melt flow rate (MFR) is 1.0 ~ 2.0g/10min (190 DEG C/2.16kg); Silane cladded type ammonium polyphosphate is purchased from Puyang Chengke Chemical Co., Ltd., and the trade mark is CK-APP103; Melamine resin cladded type ammonium polyphosphate is purchased from Puyang Chengke Chemical Co., Ltd., and the trade mark is CK-APP102; 4A molecular sieve is purchased from Guangzhou Hengbang Fine Chemical Limited Company; Twin screw extruder is purchased from Nanjing Rubber-Plastic Machinery Plant, and model is SJSH-Z-30.
embodiment 1
A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 20 parts, polypropylene 20 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 30 parts, cladded type ammonium polyphosphate 18 parts, 2.5 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 6 parts, lubricant 3 parts, 0.3 part, oxidation inhibitor and photostabilizer 0.2 part.
Wherein, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified wood powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 40 object wood powders, add 11L deionized water, after stirring 10min, add 0.15kg zinc borate or boric acid, continue to stir 45min;
(2) in another reactor, add 2.1kg trimeric cyanamide and 4L massfraction is the formalin of 36%, with glacial acetic acid, pH is transferred to 4.5, at 80 DEG C of temperature, heats 30min, obtained trimeric cyanamide methylol performed polymer;
(3) get the obtained trimeric cyanamide methylol performed polymer of 6L step (2) to be poured in the obtained system of step (1), be warmed up to 60 DEG C, after stirring 2h, with the aqueous sodium carbonate that massfraction is 5%, pH value be transferred to 6.5, filter after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 3h at 80 DEG C of temperature, then at 105 DEG C of temperature dry 6h, obtained terpolycyantoamino-formaldehyde resin modified wood powder.
Wherein, described cladded type ammonium polyphosphate is melamine resin cladded type ammonium polyphosphate (trade mark is CK-APP102), and the particle diameter of cladded type ammonium polyphosphate is 10 μm, and the polymerization degree is 1000, and phosphorus content is 28%, and nitrogen content is 20%; Described maleic anhydride stem grafting polyolefin is maleic anhydride inoculated polypropylene (trade mark is GPM200A), and the percentage of grafting of maleic anhydride stem grafting polyolefin is 5%; Described lubricant comprises dimethyl silicone oil 1 part and polyethylene wax 2 parts; Described oxidation inhibitor is antioxidant 1010; Described photostabilizer is photostabilizer GW-944.
A kind of preparation method of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 180 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
embodiment 2
A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 20 parts, polypropylene 15 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 28 parts, cladded type ammonium polyphosphate 23 parts, 1 part, 4A molecular sieve, maleic anhydride stem grafting polyolefin 8 parts, lubricant 2.5 parts, 0.5 part, oxidation inhibitor and photostabilizer 0.5 part.
Wherein, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified bamboo powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 40 object bamboo powder, add 15L deionized water, after stirring 11min, add 0.20kg zinc borate or boric acid, continue to stir 60min;
(2) in another reactor, add 2.4kg trimeric cyanamide and 3.5L massfraction is the formalin of 35%, with glacial acetic acid, pH is transferred to 5.5, at 70 DEG C of temperature, heats 45min, obtained trimeric cyanamide methylol performed polymer;
(3) get the obtained trimeric cyanamide methylol performed polymer of 5L step (2) to be poured in the obtained system of step (1), be warmed up to 70 DEG C, after stirring lh, with the aqueous sodium carbonate that massfraction is 4%, pH value be transferred to 7.5, filter after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 4h at 85 DEG C of temperature, then at 110 DEG C of temperature dry 4h, obtained terpolycyantoamino-formaldehyde resin modified wood powder or terpolycyantoamino-formaldehyde resin modified bamboo powder.
Wherein, described cladded type ammonium polyphosphate is melamine resin cladded type ammonium polyphosphate (trade mark is CK-APP102), and the particle diameter of cladded type ammonium polyphosphate is 12 μm, and the polymerization degree is 2000, and phosphorus content is 29%, and nitrogen content is 19%; Described maleic anhydride stem grafting polyolefin is maleic anhydride inoculated polypropylene (trade mark is GPM200AL), and the percentage of grafting of maleic anhydride stem grafting polyolefin is 6%; Described lubricant is dimethyl silicone oil; Described oxidation inhibitor is antioxidant 1076; Described photostabilizer is photostabilizer GW-622.
A kind of preparation method of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 185 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
embodiment 3
A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 24 parts, polypropylene 13 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 31 parts, cladded type ammonium polyphosphate 20 parts, 1.5 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 7 parts, lubricant 2.8 parts, 0.2 part, oxidation inhibitor and photostabilizer 0.4 part.
Wherein, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified bamboo powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 100 object bamboo powder, add 12.5L deionized water, after stirring 12min, add 0.15kg zinc borate or boric acid, continue to stir 50min;
(2) in another reactor, add 2.3kg trimeric cyanamide and 4.5L massfraction is the formalin of 37%, with glacial acetic acid, pH is transferred to 5.0, at 75 DEG C of temperature, heats 40min, obtained trimeric cyanamide methylol performed polymer;
(3) get the obtained trimeric cyanamide methylol performed polymer of 7L step (2) to be poured in the obtained system of step (1), be warmed up to 65 DEG C, after stirring 2h, with the aqueous sodium carbonate that massfraction is 6%, pH value be transferred to 7.0, filter after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 4h at 80 DEG C of temperature, then at 105 DEG C of temperature dry 5h, obtained terpolycyantoamino-formaldehyde resin modified bamboo powder.
Wherein, described cladded type ammonium polyphosphate is melamine resin cladded type ammonium polyphosphate (trade mark is CK-APP102), and the particle diameter of cladded type ammonium polyphosphate is 14 μm, and the polymerization degree is 3000, and phosphorus content is 30%, and nitrogen content is 18%; Described maleic anhydride stem grafting polyolefin is maleic anhydride inoculated polypropylene (trade mark is GPM200AL), and the percentage of grafting of maleic anhydride stem grafting polyolefin is 7%; Described lubricant comprises dimethyl silicone oil 2 parts and methyl phenyl silicone oil 0.8 part; Described oxidation inhibitor is irgasfos 168; Described photostabilizer is ultraviolet absorbent uv-326.
A kind of preparation method of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 190 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
embodiment 4
A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 30 parts, polypropylene 12 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 28 parts, cladded type ammonium polyphosphate 19 parts, 3 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 5 parts, lubricant 2.4 parts, 0.3 part, oxidation inhibitor and photostabilizer 0.3 part.
Wherein, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified wood powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 60 object wood powders, add 12L deionized water, after stirring 15min, add 0.18kg zinc borate or boric acid, continue to stir 60min;
(2) in another reactor, add 2.2kg trimeric cyanamide and 3.5L massfraction is the formalin of 38%, with glacial acetic acid, pH is transferred to 5.5, at 70 DEG C of temperature, heats 40min, obtained trimeric cyanamide methylol performed polymer;
(3) get the obtained trimeric cyanamide methylol performed polymer of 5L step (2) to be poured in the obtained system of step (1), be warmed up to 65 DEG C, stir l.5h, with the aqueous sodium carbonate that massfraction is 4%, pH value is transferred to 6.5, filter after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 3h at 82 DEG C of temperature, then at 110 DEG C of temperature dry 5h, obtained terpolycyantoamino-formaldehyde resin modified wood powder.
Wherein, described cladded type ammonium polyphosphate is silane cladded type ammonium polyphosphate (trade mark is CK-APP103), and the particle diameter of cladded type ammonium polyphosphate is 15 μm, and the polymerization degree is 4000, and phosphorus content is 31%, and nitrogen content is 17%; Described maleic anhydride stem grafting polyolefin is maleic anhydride inoculated polypropylene (trade mark is GPM200B), and the percentage of grafting of maleic anhydride stem grafting polyolefin is 8%; Described lubricant is stearic acid; Described oxidation inhibitor oxidation inhibitor 626; Described photostabilizer is photostabilizer GW-540.
A kind of preparation method of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 195 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
embodiment 5
A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 22 parts, polypropylene 10 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 35 parts, cladded type ammonium polyphosphate 21 parts, 2.2 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 5.4 parts, lubricant 2 parts, 0.2 part, oxidation inhibitor and photostabilizer 0.2 part.
Wherein, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified wood powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 80 object wood powders, add 14L deionized water, after stirring 13min, add 0.18kg zinc borate or boric acid, continue to stir 45min;
(2) in another reactor, add 2.3kg trimeric cyanamide and 4L massfraction is the formalin of 39%, with glacial acetic acid, pH is transferred to 5.0, at 75 DEG C of temperature, heats 40min, obtained trimeric cyanamide methylol performed polymer;
(3) get the obtained trimeric cyanamide methylol performed polymer of 6L step (2) to be poured in the obtained system of step (1), be warmed up to 65 DEG C, stir l.5h, with the aqueous sodium carbonate that massfraction is 5%, pH value is transferred to 7.0, filter after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 4h at 85 DEG C of temperature, then at 110 DEG C of temperature dry 4.5h, obtained terpolycyantoamino-formaldehyde resin modified wood powder.
Wherein, described cladded type ammonium polyphosphate is silane cladded type ammonium polyphosphate (trade mark is CK-APP103), and the particle diameter of cladded type ammonium polyphosphate is 16 μm, and the polymerization degree is 5000, and phosphorus content is 32%, and nitrogen content is 16%; Described maleic anhydride stem grafting polyolefin is maleic anhydride inoculated polypropylene (trade mark is GPM200B), and the percentage of grafting of maleic anhydride stem grafting polyolefin is 9%; Described lubricant comprises methyl phenyl silicone oil 0.4 part, polyethylene wax 0.8 part and calcium stearate 0.8 part; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1 antioxidant 1010 and irgasfos 168; Described photostabilizer is ultraviolet absorbent UV-531.
A kind of preparation method of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 200 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
embodiment 6
A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 28 parts, polypropylene 16 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 29 parts, cladded type ammonium polyphosphate 18 parts, 2 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 5 parts, lubricant 2.2 parts, 0.5 part, oxidation inhibitor and photostabilizer 0.3 part.
Wherein, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified wood powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 100 object wood powders, add 10L deionized water, after stirring 15min, add 0.20kg zinc borate or boric acid, continue to stir 55min;
(2) in another reactor, add 2.4kg trimeric cyanamide and 4.5L massfraction is the formalin of 37%, with glacial acetic acid, pH is transferred to 5.5, at 80 DEG C of temperature, heats 45min, obtained trimeric cyanamide methylol performed polymer;
(3) get the obtained trimeric cyanamide methylol performed polymer of 7L step (2) to be poured in the obtained system of step (1), be warmed up to 60 DEG C, after stirring lh, with the aqueous sodium carbonate that massfraction is 6%, pH value be transferred to 7.5, filter after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 3h at 80 DEG C of temperature, then at 110 DEG C of temperature dry 6h, obtained terpolycyantoamino-formaldehyde resin modified wood powder.
Wherein, described cladded type ammonium polyphosphate is silane cladded type ammonium polyphosphate (trade mark is CK-APP103), and the particle diameter of cladded type ammonium polyphosphate is 18 μm, and the polymerization degree is 3500, and phosphorus content is 33%, and nitrogen content is 15%; Described maleic anhydride stem grafting polyolefin is maleic anhydride graft high density polyethylene(HDPE) (trade mark is EPA830H), and the percentage of grafting of maleic anhydride stem grafting polyolefin is 10%; Described lubricant is Magnesium Stearate; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1 antioxidant 1010 and irgasfos 168; Described photostabilizer is photostabilizer GW-770.
A kind of preparation method of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 190 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
embodiment 7
A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material, described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 25 parts, polypropylene 18 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 33 parts, cladded type ammonium polyphosphate 20 parts, 2.1 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 4 parts, lubricant 2 parts, 0.4 part, oxidation inhibitor and photostabilizer 0.5 part.
Wherein, described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified wood powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 70 object wood powders, add 13L deionized water, after stirring 12.5min, add 0.20kg zinc borate or boric acid, continue to stir 55min;
(2) in another reactor, add 2.2kg trimeric cyanamide and 4.0L massfraction is the formalin of 38%, with glacial acetic acid, pH is transferred to 4.5, at 80 DEG C of temperature, heats 30min, obtained trimeric cyanamide methylol performed polymer;
(3) get the obtained trimeric cyanamide methylol performed polymer of 6L step (2) to be poured in the obtained system of step (1), be warmed up to 70 DEG C, after stirring lh, with the aqueous sodium carbonate that massfraction is 5%, pH value be transferred to 6.5, filter after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 3.5h at 82 DEG C of temperature, then at 108 DEG C of temperature dry 5.5h, obtained terpolycyantoamino-formaldehyde resin modified wood powder.
Wherein, described cladded type ammonium polyphosphate is melamine resin cladded type ammonium polyphosphate (trade mark is CK-APP102), and the particle diameter of cladded type ammonium polyphosphate is 20 μm, and the polymerization degree is 5000, and phosphorus content is 34%, and nitrogen content is 14%; Described maleic anhydride stem grafting polyolefin is maleic anhydride graft high density polyethylene(HDPE) (trade mark is EPA830H), and the percentage of grafting of maleic anhydride stem grafting polyolefin is 11%; Described lubricant comprises methyl phenyl silicone oil 0.4 part, polyethylene wax 0.8 part, sodium stearate 0.8 part; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1 antioxidant 1010 and irgasfos 168; Described photostabilizer is photostabilizer GW-770.
A kind of preparation method of fire retardant PBT with no halogen/PP base wood-plastic composite material, comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 185 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
Fire retardant PBT with no halogen prepared by embodiment 1-7/PP base wood-plastic composite material pellet is injection molded into test standard batten by standard size.According to the fire-retardant rank of UL94-2009 standard test, according to GB/T2406.2-2009 standard test limiting oxygen index(LOI), according to ASTMD638-08 standard test tensile strength, according to ASTMD256-06a standard test unnotched impact strength, according to ASTMD790-03 standard test flexural strength, according to ASTMD648-07 standard test heat-drawn wire, the results of property of embodiment 1-7 is as shown in table 1.
Comparative example 1
Be that in the Chinese invention patent of 201010179160.9, embodiment 2 is comparative example with application number, its main formula consists of: 31.9% homopolymerization PP, 30%100 order bamboo powder, 5%EPDM, 5%EPDM-g-MAH, 10% red phosphor masterbatch, 10% super fine magnesium hydroxide, other 8.1%, the performance of obtained wood plastic composite is as shown in table 1.
The performance of wood plastic composite prepared by table 1 embodiment 1 ~ 7 and comparative example 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 |
| Tensile strength (MPa) | 39.4 | 37.9 | 36.3 | 42.8 | 35.5 | 43.6 | 38.7 | 28.5 |
| Unnotched impact strength (J/m) | 173.7 | 194.1 | 198.4 | 164.0 | 198.8 | 157.3 | 179.2 | 292 |
| Flexural strength (MPa) | 49.0 | 47.5 | 48.8 | 49.8 | 47.0 | 51.0 | 42.0 | 41.4 |
| Modulus in flexure (GPa) | 3.54 | 3.32 | 3.21 | 3.58 | 3.23 | 3.62 | 3.45 | 2.67 |
| Heat-drawn wire (0.455Mpa, DEG C) | 146.9 | 145.6 | 144.8 | 147.9 | 143.1 | 149.1 | 145.3 | — |
| Limiting oxygen index(LOI) (%) | 29.3 | 30.8 | 30.0 | 30.5 | 31.6 | 29.2 | 29.4 | — |
| UL-94 flame retardant rating (1.6mm) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
As can be seen from Table 1, fire retardant PBT with no halogen of the present invention/PP base wood-plastic composite material, only adopt the cladded type ammonium polyphosphate flame retardant of 18-23 part, the test of 1.6mm batten vertical combustion is just by UL-94V-0 level, reach in prior art the level (comparative example 1) adopting red phosphor masterbatch and super fine magnesium hydroxide compositional flame-retardant, excellent fireproof performance; Fire retardant PBT with no halogen of the present invention/PP base wood-plastic composite material mechanical strength is high, when the consumption of cladded type ammonium polyphosphate is 20 parts, vertical combustion test have passed UL-94V-0 level, tensile strength reaches 36.3MPa, flexural strength reaches 48.8MPa, and both are respectively than the comparative example 1 high 27% and 18% of same amount of flame-retardant agent, and mechanical property is better, and heat-drawn wire is 144.8 DEG C, life-time service temperature Gao Keda 120 DEG C.Fire retardant PBT with no halogen of the present invention/PP base wood-plastic composite material is while obtaining good flame retardant properties as can be seen here, and comprehensive mechanical property, life-time service temperature are high, and using value is large.
Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. fire retardant PBT with no halogen/PP base wood-plastic composite material, is characterized in that: described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 20-30 part, polypropylene 10-20 part, terpolycyantoamino-formaldehyde resin modified plant fibers 28-35 part, cladded type ammonium polyphosphate 18-23 part, 4A molecular sieve 1-3 part, maleic anhydride stem grafting polyolefin 4-8 part, lubricant 2-3 part, oxidation inhibitor 0.2-0.5 part and photostabilizer 0.2-0.5 part.
2. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, is characterized in that: described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 22-28 part, polypropylene 12-18 part, terpolycyantoamino-formaldehyde resin modified plant fibers 29-33 part, cladded type ammonium polyphosphate 19-21 part, 4A molecular sieve 1.5-2.5 part, maleic anhydride stem grafting polyolefin 5-7 part, lubricant 2.2-2.8 part, oxidation inhibitor 0.2-0.4 part and photostabilizer 0.2-0.4 part.
3. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, is characterized in that: described wood plastic composite comprises the raw material of following weight part: polybutylene terephthalate 25 parts, polypropylene 15 parts, terpolycyantoamino-formaldehyde resin modified plant fibers 31 parts, cladded type ammonium polyphosphate 20 parts, 2 parts, 4A molecular sieve, maleic anhydride stem grafting polyolefin 6 parts, lubricant 2.5 parts, 0.3 part, oxidation inhibitor and photostabilizer 0.3 part.
4. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, it is characterized in that: described terpolycyantoamino-formaldehyde resin modified plant fibers is terpolycyantoamino-formaldehyde resin modified wood powder or terpolycyantoamino-formaldehyde resin modified bamboo powder, and its preparation method comprises the steps:
(1) 1kg particle diameter is put into reactor at 40-100 object wood powder or bamboo powder, add 10-15L deionized water, after stirring 10-15min, add 0.15-0.20kg zinc borate or boric acid, continue to stir 45-60min;
(2) in another reactor, add 2.1-2.4kg trimeric cyanamide and 3.5-4.5L massfraction is the formalin of 35-39%, with glacial acetic acid, pH is transferred to 4.5-5.5, at 70-80 DEG C of temperature, heats 30-45min, obtained trimeric cyanamide methylol performed polymer;
(3) getting the obtained trimeric cyanamide methylol performed polymer of 5-7L step (2) is poured in the obtained system of step (1), be warmed up to 60-70 DEG C, after stirring l-2h, with the aqueous sodium carbonate that massfraction is 4-6%, pH value is transferred to 6.5-7.5, filters after being down to room temperature, wash; Gained filter cake is put into loft drier, first dry 3-4h at 80-85 DEG C of temperature, then at 105-110 DEG C of temperature dry 4-6h, obtained terpolycyantoamino-formaldehyde resin modified wood powder or terpolycyantoamino-formaldehyde resin modified bamboo powder.
5. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, it is characterized in that: described cladded type ammonium polyphosphate is silane cladded type ammonium polyphosphate or melamine resin cladded type ammonium polyphosphate, the particle diameter of cladded type ammonium polyphosphate is 10-20 μm, the polymerization degree is 1000-5000, Lin Han Liang≤28%, Dan Han Liang≤14%.
6. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, it is characterized in that: described maleic anhydride stem grafting polyolefin is maleic anhydride inoculated polypropylene and/or maleic anhydride graft high density polyethylene(HDPE), and the percentage of grafting of maleic anhydride stem grafting polyolefin is more than or equal to 5%.
7. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, is characterized in that: described lubricant is at least one in dimethyl silicone oil, methyl phenyl silicone oil, polyethylene wax, stearic acid and stearate soap; Described stearate soap is at least one in calcium stearate, Magnesium Stearate and sodium stearate.
8. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, is characterized in that: described oxidation inhibitor is phenolic antioxidant and/or phosphite ester kind antioxidant; Described phenolic antioxidant is antioxidant 1010 and/or antioxidant 1076; Described phosphite ester kind antioxidant is irgasfos 168 and/or oxidation inhibitor 626.
9. a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material according to claim 1, is characterized in that: described photostabilizer is at least one in photostabilizer GW-770, ultraviolet absorbent UV-531, UV light absorber UV-329, photostabilizer GW-540, ultraviolet absorbent uv-326, photostabilizer GW-622 and photostabilizer GW-944.
10. the preparation method of a kind of fire retardant PBT with no halogen/PP base wood-plastic composite material as described in any one of claim 1-9, it is characterized in that: comprise the steps: to take each raw material by the weight part of above-mentioned raw materials, drop in high-speed mixer and mix, by twin screw extruder melting at 180-200 DEG C of temperature, mixing, extrude, cool, pelletizing and drying, obtained fire retardant PBT with no halogen/PP base wood-plastic composite material.
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| CN106243686A (en) * | 2016-08-26 | 2016-12-21 | 桐城市中汇塑业有限公司 | A kind of acidifying graphite plastic composite |
| CN106280316A (en) * | 2016-08-26 | 2017-01-04 | 桐城市中汇塑业有限公司 | A kind of PP PBT plastic alloy composite |
| CN106496971A (en) * | 2016-11-18 | 2017-03-15 | 无锡明盛纺织机械有限公司 | A kind of engineering plastic materials containing bamboo fibre and preparation method |
| CN106633685A (en) * | 2016-09-30 | 2017-05-10 | 无锡市明盛强力风机有限公司 | PBT engineering plastic material and preparation method |
| CN112341765A (en) * | 2020-10-29 | 2021-02-09 | 天津金发新材料有限公司 | PBT/PP composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106243686A (en) * | 2016-08-26 | 2016-12-21 | 桐城市中汇塑业有限公司 | A kind of acidifying graphite plastic composite |
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| CN118359905A (en) * | 2024-05-07 | 2024-07-19 | 江苏顺仕净化设备有限公司 | Plastic-wood composite material plate with adsorption purification function and preparation method thereof |
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