CN112480610A - High-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material and preparation method thereof - Google Patents

High-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material and preparation method thereof Download PDF

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CN112480610A
CN112480610A CN202011352789.9A CN202011352789A CN112480610A CN 112480610 A CN112480610 A CN 112480610A CN 202011352789 A CN202011352789 A CN 202011352789A CN 112480610 A CN112480610 A CN 112480610A
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halogen
pbt
retardant
free flame
basalt fiber
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王飞
张超
安朋
叶士兵
肖军华
丁正亚
杨波
吴国峰
李晓轩
罗忠富
夏建盟
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Shanghai Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
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Shanghai Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
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Priority to CN202011352789.9A priority Critical patent/CN112480610A/en
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Abstract

The invention relates to a high-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material and a preparation method thereof. The material is formed by blending long-fiber basalt fiber reinforced PBT master batch and halogen-free flame-retardant toughening master batch; the long-fiber basalt fiber reinforced PBT master batch comprises the following components: long basalt fibers, PBT resin, a heat stabilizer and a lubricant; the halogen-free flame-retardant toughening master batch comprises the following components: PBT resin, halogen-free flame retardant, flame-retardant synergist, toughening agent, heat stabilizer and lubricant. The PBT material has good flame retardant property and better impact property. The method has the advantages of simple preparation process, low cost and environmental friendliness, and further widens the application scene of the PBT material.

Description

High-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material and a preparation method thereof.
Background
The long fiber reinforced material is a reinforced material with reinforcing fibers arranged in one direction and the length of the reinforcing fibers is the same as that of the resin granules, and compared with the conventional short fiber reinforced material, the long fiber reinforced material has more excellent mechanical property, fatigue resistance, creep resistance and the like, and particularly has extremely excellent impact resistance.
The basalt fiber is a novel inorganic environment-friendly green high-performance fiber, and is one of four major high-performance fibers which are intensively developed in China in the future. The basalt fiber has good stability, excellent electrical insulation, corrosion resistance, high temperature resistance and good flame retardant property. The basalt continuous fiber has been widely applied in various aspects such as fiber reinforced composite materials, friction materials, shipbuilding materials, heat insulation materials, automobile industry, high-temperature filter fabrics, protection fields and the like.
Polybutylene terephthalate (PBT), a polyester produced by polycondensation of terephthalic acid and 1, 4-butanediol. The most important thermoplastic polyester, one of five major engineering plastics. PBT is a milky translucent to opaque, semi-crystalline thermoplastic polyester. Has high heat resistance, long-term work at 140 ℃, toughness, fatigue resistance, self-lubrication and low friction coefficient. It is not resistant to strong acid and alkali, and can resist organic solvent, and is flammable and can be decomposed at high temp. Because of these excellent properties, they are widely used in the fields of automobiles, mechanical equipment, precision instrument parts, electronic and electrical appliances, textiles, etc., but in the fields of electronics, electrical and automotive applications, the materials need excellent flame retardant properties and mechanical properties. The PBT material has high strength but poor toughness, and the impact performance of the material is further reduced after the conventional flame retardant is added.
Chinese patent CN 107298832A discloses a basalt fiber reinforced polybutylene terephthalate composite material and a preparation method thereof, wherein basalt fibers are subjected to surface modification treatment by using a modifier, so that the fiber surface roughness is increased, and a large number of active sites and active groups are formed, thereby increasing the compatibility of the basalt fibers and the polybutylene terephthalate material, and the basalt fibers can be chemically bonded and mechanically riveted with the polybutylene terephthalate material, and then are compounded with the polybutylene terephthalate material to obtain the basalt fiber reinforced polybutylene terephthalate composite material with excellent performance.
Chinese patent CN 108164934A discloses a basalt fiber reinforced PBT composite material and application thereof, the material is obtained by producing raw materials which are composed of modified basalt fiber, antimony trioxide or siloxane/sulfonate composite flame-retardant PBT resin master batch, a coupling agent, an ethylene propylene rubber toughening agent and high-mesh talcum powder and is used for preparing a bicycle component by mould pressing. However, in the patent, the raw materials consisting of the flame-retardant PBT resin master batch, the coupling agent, the ethylene propylene rubber toughening agent and the high-mesh talcum powder are directly melted and extruded to an impregnation die head through a double-screw extruder at high temperature, the melt in the extruder is polyethylene terephthalate added with the flame retardant and the toughening agent, and finally, the continuous basalt fiber reinforced polyethylene terephthalate which is drawn and extruded is cut into granules of 4-25mm by a granulator. The disadvantages of this preparation method are: (1) the production efficiency is low: extruding all raw materials through an extruder die head (wherein the melt is thermoplastic resin containing a flame retardant and a toughening agent), extruding the raw materials into an impregnation die for impregnation, and performing pultrusion and dicing through a tractor and a dicing cutter, wherein the production speed is relatively low due to the reduction of the fluidity of the raw materials caused by the addition of the toughening agent; (2) the process control is difficult, and the product quality can not be ensured: if the impregnation die temperature is low, the fiber experiences high tension as it passes through the die, and is easily damaged, resulting in frequent production interruptions; if the temperature of the dipping die head is increased, the flame retardant is easily degraded after being subjected to high temperature for a long time, so that the product quality cannot be ensured; (3) the used flame retardant is antimony trioxide or siloxane/sulfonate composite flame retardant, and the flame retardant has high cost and is not beneficial to wide application.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material and a preparation method thereof, so as to overcome the defects of low production efficiency, difficult process control, high cost and the like of the basalt fiber reinforced PBT material in the prior art.
The invention provides a high-impact-resistance long basalt fiber reinforced halogen-free flame-retardant PBT material, which is formed by blending long-fiber basalt fiber reinforced PBT master batch and halogen-free flame-retardant toughening master batch;
the long-fiber basalt fiber reinforced PBT master batch comprises the following components in percentage by weight: 20 to 60 percent of long basalt fiber, 38 to 79.6 percent of PBT resin, 0.2 to 1 percent of heat stabilizer and 0.2 to 1 percent of lubricant;
the halogen-free flame-retardant toughening master batch comprises the following components in percentage by weight: 14.6 to 92 percent of PBT resin, 5 to 50 percent of halogen-free flame retardant, 1 to 20 percent of flame retardant synergist, 0 to 15 percent of toughening agent, 0.2 to 1 percent of heat stabilizer and 0.2 to 1 percent of lubricant.
The weight percentage of the long basalt fibers in the PBT material is 5-50%.
The melt mass flow rate of the PBT resin in the PBT master batch is 20g/10min-100g/10 min. Wherein the melt mass flow rate test conditions are as follows: 250 ℃ and 2.16 kg.
The melt mass flow rate of the PBT resin in the halogen-free flame-retardant toughening master batch is 5g/10min-100g/10 min. Wherein the melt mass flow rate test conditions are: 250 ℃ and 2.16 kg.
The halogen-free flame retardant is at least one of melamine phosphate, red phosphorus, pentaerythritol phosphate and hypophosphite.
The flame-retardant synergist is at least one of zinc borate, titanium dioxide and hydrotalcite.
The toughening agent is at least one of ethylene-butyl acrylate-glycidyl methacrylate copolymer and copolymer of ethylene and methyl acrylate.
The heat stabilizer is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, pentaerythritol tetra (3-lauryl thiopropionate) and tris [2, 4-di-tert-butylphenyl ] phosphite.
The lubricant is at least one of ethylene bis stearamide, E wax, calcium stearate and pentaerythritol tetrastearate.
The invention also provides a preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material, which comprises the following steps:
(1) adding PBT resin, a heat stabilizer and a lubricant into an extruder, melting and uniformly mixing, extruding into an impregnation die head, impregnating long basalt fiber in the impregnation die head, pulling out, and sequentially cooling, drawing and granulating to obtain long fiber basalt fiber reinforced PBT master batch;
(2) adding PBT resin, a halogen-free flame retardant, a flame-retardant synergist, a toughening agent, a heat stabilizer and a lubricant into a double-screw extruder to be melted and uniformly mixed, and then extruding and granulating to obtain halogen-free flame-retardant toughening master batches;
(3) and (2) uniformly mixing the long-fiber basalt fiber reinforced PBT master batch and the halogen-free flame retardant toughening master batch in the step (1) to obtain the high-impact-resistance long basalt fiber reinforced halogen-free flame retardant PBT material.
The length of the long-fiber basalt fiber reinforced PBT master batch in the step (1) is 3-25 mm.
The proportion of the long-fiber basalt fiber reinforced PBT master batch to the halogen-free flame-retardant toughening master batch in the step (3) is specifically determined according to the use requirement and the content of the basalt fiber.
The invention also provides application of the high-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material in the fields of automobiles, household appliances, tools and the like.
Advantageous effects
The invention adopts the mode of mixing the long basalt fiber reinforced PBT resin master batch and the halogen-free flame-retardant toughening master batch, and the method has the advantages of simple preparation process, high production efficiency, good process stability, controllable quality and environmental friendliness.
The raw materials (such as the flame retardant and the flame retardant synergist) adopted by the invention have lower cost, and simultaneously, because the basalt fiber has excellent flame retardant property, the addition amount of the flame retardant is reduced compared with the traditional glass fiber reinforced halogen-free flame retardant PBT material, thereby further reducing the cost.
According to the invention, the toughness of the halogen-free flame-retardant PBT material is further improved in a long basalt fiber and toughening agent composite mode, and compared with a short basalt fiber reinforced halogen-free flame-retardant PBT material, the toughness of the material is greatly improved, other mechanical strength of the material is also improved, and the application field and scene of the PBT material are widened.
The PBT material disclosed by the invention not only has good flame retardant property, but also has good impact property and high strength.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The examples of the invention and comparative examples relate to the following sources of raw materials, but are not limited to the following:
PBT GX112, GX 121: characterizing chemical fibers from a ceremony;
PBT 1084, 1100A: from southeast Star;
long basalt fiber: from Sichuan space Tuoxing basalt industries Ltd: BC13-68 × 1 × 2-S68;
halogen-free flame retardant: from clainn: OP1230 (hypophosphite), budemmheim: BUDIT 3141 (melamine polyphosphate); FR9950KF (red phosphorus), cantonese PEPA (pentaerythritol phosphate);
flame retardant synergist: from rituo, santai HT-207 (zinc borate); japanese Hokka NAOX-33 (hydrotalcite), Hangzhou Wanjing new material VK-T03 (titanium dioxide);
a toughening agent: from dupont: ELVALOY PTW (ethylene-butyl acrylate-glycidyl methacrylate copolymer); dupont ELVALOY AC 1125 (ethylene and methyl acrylate copolymer);
thermal stabilizer: from Rianlong, RIAOX 412S (pentaerythritol tetrakis (3-laurylthiopropionate)), Shandong Sanfeng chemical: SONOX 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], SONOX 168 (tris [2, 4-di-tert-butylphenyl ] phosphite), and the like;
lubricant: LOXIOL P861/3.5, DEITACEAN, PETS-AP, GLYCOLUBE-P, LOXAN, USA (pentaerythritol tetrastearate), and Indonesian EBS B50 (ethylene bisstearamide).
Example 1
Preparing long basalt fiber reinforced PBT resin master batch:
adding 49% of PBT 1084, 0.5% of heat stabilizer (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.5% of lubricant (pentaerythritol tetrastearate) into an extruder according to the weight ratio of 1:1, melting and uniformly mixing, extruding into an impregnation die head (the processing temperature is the conventional process in the field, the processing temperature is 100-240 ℃, the die temperature is 250 ℃), drawing the long basalt fiber through the impregnation die head, cooling, drawing and granulating in sequence to prepare the long basalt fiber reinforced PBT resin master batch (the length of the fiber and the particle is equal to 11mm), wherein the mass of the long basalt fiber is 50%.
Preparing halogen-free flame-retardant toughening master batch:
uniformly mixing 56.5 percent of PBT 1100A, 20 percent of halogen-free flame retardant (melamine phosphate BUDIT 3141 and pentaerythritol phosphate are compounded according to the weight ratio of 1:1), 15 percent of flame-retardant synergist (zinc borate and titanium dioxide are compounded according to the weight ratio of 1:1), 0.5 percent of heat stabilizer (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [ 2.4-di-tert-butylphenyl ] phosphite) according to the weight ratio of 1:1), 0.5 percent of lubricant (pentaerythritol tetrastearate) and 7.5 percent of toughener (ethylene-butyl acrylate-glycidyl methacrylate copolymer and copolymer of ethylene and methyl acrylate are compounded according to the weight ratio of 1: 2), and carrying out melt granulation in an extruder (the processing temperature is 100-240 ℃, and the processing temperature is the conventional process in the field), obtaining the halogen-free flame-retardant toughening master batch.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
mixing the long basalt fiber reinforced PBT resin master batch and the halogen-free flame-retardant toughening master batch according to the weight ratio of 3:2 to prepare the required high-impact long basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material. In the final material, the PBT content is 52%, the basalt fiber content is 30%, the halogen-free flame retardant content is 8%, the flame-retardant synergist content is 6%, the toughening agent content is 3%, the heat stabilizer content is 0.5%, and the lubricant content is 0.5%, wherein the percentages are weight percentages.
Example 2
The preparation of the long basalt fiber reinforced PBT resin master batch is the same as that of the example 1.
Preparing halogen-free flame-retardant toughening master batch:
uniformly mixing 44% of PBT 1084, 30% of a halogen-free flame retardant (hypophosphite OP1230), 20% of a flame-retardant synergist (zinc borate), 0.5% of a heat stabilizer (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris [ 2.4-di-tert-butylphenyl ] phosphite in a weight ratio of 1:1), 0.5% of a lubricant (pentaerythritol tetrastearate) and 5% of a toughening agent (ethylene-butyl acrylate-glycidyl methacrylate copolymer), and performing melt granulation in an extruder (the processing temperature is 100-240 ℃, and the processing temperature is a conventional process in the field) to obtain the halogen-free flame-retardant toughening master batch.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
the long basalt fiber reinforced PBT resin master batch and the halogen-free flame retardant toughening master batch are mixed according to the weight ratio of 4:1 to prepare the required high-impact long basalt fiber reinforced halogen-free flame retardant polybutylene terephthalate material. In the final material, the PBT content is 48%, the basalt fiber content is 40%, the halogen-free flame retardant content is 6%, the flame-retardant synergist content is 4%, the toughening agent content is 1%, the heat stabilizer content is 0.5%, and the lubricant content is 0.5%, wherein the percentages are weight percentages.
Example 3
Preparing long basalt fiber reinforced PBT resin master batch:
adding 39% of PBT GX112, 0.5% of heat stabilizer (pentaerythritol tetra (3-lauryl thiopropionate) and tris [ 2.4-di-tert-butylphenyl ] phosphite) which are compounded according to the weight ratio of 1:1 and 0.5% of lubricant (pentaerythritol tetrastearate) into an extruder, melting and uniformly mixing, extruding into an impregnation die head (the processing temperature is the conventional process in the field, the processing temperature is 100-240 ℃, the die temperature is 250 ℃), drawing long basalt fibers through the impregnation die head, cooling, drawing and granulating in sequence to prepare long basalt fiber reinforced PBT resin master batches (the length of the fibers and the particles is equal and 11mm), wherein the mass of the long basalt fibers is 60%.
The preparation of the halogen-free flame retardant toughening master batch is the same as that of the example 2.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
the long basalt fiber reinforced PBT resin master batch and the halogen-free flame retardant toughening master batch are mixed according to the weight ratio of 83:17 to prepare the required high-impact long basalt fiber reinforced halogen-free flame retardant polybutylene terephthalate material. In the final material, the PBT content is 39.85%, the basalt fiber content is 49.8%, the halogen-free flame retardant content is 5.1%, the flame-retardant synergist content is 3.4%, the toughening agent content is 0.85%, the heat stabilizer content is 0.5%, and the lubricant content is 0.5%, wherein the percentages are weight percentages.
Example 4
Preparing long basalt fiber reinforced PBT resin master batch:
adding 58% of PBT 1084, 1% of heat stabilizer (pentaerythritol tetra (3-lauryl thiopropionate) and tris [2, 4-di-tert-butylphenyl ] phosphite) and 1% of lubricant (ethylene bis stearamide) into an extruder according to the weight ratio of 1:1, melting and uniformly mixing, extruding into an impregnation die head (the processing temperature is the conventional process in the field, the processing temperature is 100-240 ℃, the die temperature is 250 ℃), drawing the long basalt fiber through the impregnation die head, and then sequentially cooling, drawing and granulating to prepare the long basalt fiber reinforced PBT resin master batch (the length of the fiber and the particle is equal to 11mm), wherein the mass of the long basalt fiber is 40%.
The preparation of the halogen-free flame retardant toughening master batch is the same as that of the example 1.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
mixing the long basalt fiber reinforced PBT resin master batch and the halogen-free flame-retardant toughening master batch according to the weight ratio of 1:1 to prepare the required high-impact long basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material. In the final material, the PBT content is 57.25%, the basalt fiber content is 20%, the halogen-free flame retardant content is 10%, the flame-retardant synergist content is 7.5%, the toughening agent content is 3.75%, the heat stabilizer content is 0.75%, and the lubricant content is 0.75%, wherein the percentages are weight percentages.
Example 5
The preparation of the long basalt fiber reinforced PBT resin master batch is the same as that of the example 4.
Preparing halogen-free flame-retardant toughening master batch:
55 percent of PBT GX121, 20 percent of halogen-free flame retardant (melamine phosphate BUDIT 3141 and hypophosphite OP1230 according to the weight ratio of 3:2), 15 percent of flame-retardant synergist (zinc borate and hydrotalcite according to the weight ratio of 2:1), 1 percent of heat stabilizer (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite are compounded according to the weight ratio of 1:1), 1% of lubricant (pentaerythritol tetrastearate) and 8% of toughening agent (ethylene-butyl acrylate-glycidyl methacrylate copolymer and copolymer of ethylene and methyl acrylate are compounded according to the weight ratio of 1:1), and the mixture is melted and granulated in an extruder (the processing temperature is the conventional process in the field, and the processing temperature is 100-240 ℃) to obtain the halogen-free flame-retardant toughening master batch.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
mixing the long basalt fiber reinforced PBT resin master batch and the halogen-free flame-retardant toughening master batch according to the weight ratio of 1:3 to prepare the required high-impact long basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material. In the final material, the PBT content is 55.75%, the basalt fiber content is 10%, the halogen-free flame retardant content is 15%, the flame-retardant synergist content is 11.25%, the heat stabilizer content is 1%, the lubricant content is 1%, and the toughening agent content is 6%, wherein the percentages are weight percentages.
Example 6
Preparing long basalt fiber reinforced PBT resin master batch:
adding 78% of PBT GX112, 1% of heat stabilizer (pentaerythritol tetra (3-lauryl thiopropionate) and tris [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 1:1) and 1% of lubricant (ethylene bis-stearamide and pentaerythritol tetrastearate in a weight ratio of 1:1) into an extruder, melting and uniformly mixing, extruding into an impregnation die head (the processing temperature is the conventional process in the field, the processing temperature is 100-240 ℃, the die temperature is 250 ℃), drawing long basalt fibers through the impregnation die head, then sequentially cooling, drawing and granulating to prepare long basalt fiber reinforced PBT resin master batches (the fibers and the granules are equal in length and 11mm in length), wherein the mass of the long basalt fibers is 20%.
Preparing halogen-free flame-retardant toughening master batch:
41 percent of PBT GX112, 30 percent of halogen-free flame retardant (melamine phosphate BUDIT 3141 and red phosphorus in a weight ratio of 2:1), 12 percent of flame-retardant synergist (zinc borate and titanium dioxide in a weight ratio of 1:1), 1 percent of heat stabilizer (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 1:1), 1% of lubricant (pentaerythritol tetrastearate) and 15% of toughening agent (ethylene-butyl acrylate-glycidyl methacrylate copolymer and copolymer of ethylene and methyl acrylate are compounded according to the weight ratio of 1:1), and the mixture is melted and granulated in an extruder (the processing temperature is 100-240 ℃, and the processing temperature is the conventional process in the field) to obtain the halogen-free flame retardant toughening master batch.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
mixing the long basalt fiber reinforced PBT resin master batch and the halogen-free flame-retardant toughening master batch according to the weight ratio of 1:3 to prepare the required high-impact long basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material. In the final material, the PBT content is 50.25%, the basalt fiber content is 5%, the halogen-free flame retardant content is 22.5%, the flame-retardant synergist content is 9%, the toughening agent content is 11.25%, the heat stabilizer content is 1%, and the lubricant content is 1%, wherein the percentages are weight percentages.
Example 7
The preparation of the long basalt fiber reinforced PBT resin master batch is the same as that of the example 6.
Preparing halogen-free flame-retardant toughening master batch:
14.6 percent of PBT GX112, 50 percent of halogen-free flame retardant (melamine phosphate and red phosphorus are mixed according to the weight ratio of 2:1), 20 percent of flame-retardant synergist (zinc borate and titanium dioxide are mixed according to the weight ratio of 1:1), 0.2 percent of heat stabilizer (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [ 2.4-di-tert-butylphenyl ] phosphite are mixed according to the weight ratio of 1:1), 0.2% of lubricant (pentaerythritol tetrastearate) and 15% of toughening agent (ethylene-butyl acrylate-glycidyl methacrylate copolymer and copolymer of ethylene and methyl acrylate are compounded according to the weight ratio of 1:1), and the mixture is melted and granulated in an extruder (the processing temperature is the conventional process in the field, and the processing temperature is 100-240 ℃) to obtain the halogen-free flame retardant toughening master batch.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
the long basalt fiber reinforced PBT resin master batch and the halogen-free flame retardant toughening master batch are mixed according to the weight ratio of 3:1 to prepare the required high-impact long basalt fiber reinforced halogen-free flame retardant polybutylene terephthalate material. In the final material, the PBT content is 62.15%, the basalt fiber content is 15%, the halogen-free flame retardant content is 12.5%, the flame-retardant synergist content is 5%, the toughening agent content is 3.75%, the heat stabilizer content is 0.8%, and the lubricant content is 0.8%, wherein the percentages are weight percentages.
Example 8
The preparation of the long basalt fiber reinforced PBT resin master batch is the same as that of the example 3.
Preparing halogen-free flame-retardant toughening master batch:
92 percent of PBT GX112, 5 percent of halogen-free flame retardant (melamine phosphate and red phosphorus are mixed according to the weight ratio of 2:1), 1 percent of flame-retardant synergist (zinc borate and titanium dioxide are mixed according to the weight ratio of 1:1), 0.5 percent of heat stabilizer (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [ 2.4-di-tert-butylphenyl ] phosphite are mixed according to the weight ratio of 1:1), 0.5 percent of lubricant (pentaerythritol tetrastearate) and 1 percent of flexibilizer (ethylene-butyl acrylate-glycidyl methacrylate copolymer and copolymer of ethylene and methyl acrylate are compounded according to the weight ratio of 1:1) are evenly mixed, and are melted and granulated in an extruder (the processing temperature is 100-240 ℃, the processing temperature is the conventional process in the field) to obtain the halogen-free flame retardant toughening master batch.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
the long basalt fiber reinforced PBT resin master batch and the halogen-free flame retardant toughening master batch are mixed according to the weight ratio of 5:1 to prepare the required high-impact long basalt fiber reinforced halogen-free flame retardant polybutylene terephthalate material. In the final material, the PBT content is 47.77%, the basalt fiber content is 50%, the halogen-free flame retardant content is 0.83%, the flame retardant synergist content is 0.2%, the toughening agent content is 0.2%, the heat stabilizer content is 0.5%, and the lubricant content is 0.5%, wherein the percentages are weight percentages.
Example 9
The preparation of the long basalt fiber reinforced PBT resin master batch is the same as that of the example 3.
Preparing halogen-free flame-retardant toughening master batch:
uniformly mixing 63% of PBT GX121, 20% of a halogen-free flame retardant (melamine phosphate BUDIT 3141 and hypophosphite OP1230 according to a weight ratio of 3:2), 15% of a flame-retardant synergist (zinc borate and hydrotalcite according to a weight ratio of 2:1), 1% of a heat stabilizer (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite according to a weight ratio of 1:1) and 1% of a lubricant (pentaerythritol tetrastearate), and performing melt granulation in an extruder (the processing temperature is the conventional process in the field, and the processing temperature is 100-240 ℃) to obtain the halogen-free flame-retardant toughening master batch.
The preparation method of the high-impact-length basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material comprises the following steps:
the long basalt fiber reinforced PBT resin master batch and the halogen-free flame retardant toughening master batch are mixed according to the weight ratio of 3:2 to prepare the required high-impact long basalt fiber reinforced halogen-free flame retardant polybutylene terephthalate material. In the final material, the PBT content is 48.6%, the basalt fiber content is 36%, the halogen-free flame retardant content is 8%, the flame-retardant synergist content is 6%, the heat stabilizer content is 0.7%, and the lubricant content is 0.7%, wherein the percentages are weight percentages.
Comparative example 1
Uniformly mixing raw materials with the PBT content of 52%, the basalt fiber content of 30%, the halogen-free flame retardant content of 8%, the flame-retardant synergist content of 6%, the toughening agent content of 3%, the heat stabilizer content of 0.5% and the lubricant content of 0.5%, adding the mixture into a double-screw extruder (the processing temperature is 100-240 ℃, and the processing temperature is a conventional process in the field), and extruding and granulating the mixture into a 30% short basalt fiber content reinforced halogen-free flame-retardant PBT material (the fiber length is 0.1-0.6 mm, and the particle length is 3mm) after melt extrusion and cooling of the double-screw extruder. The percentage contents are all weight percentages. The raw materials were the same as in example 1.
Comparative example 2
Uniformly mixing raw materials with 55.75% of PBT, 10% of basalt fiber, 15% of halogen-free flame retardant, 11.25% of flame-retardant synergist, 1% of heat stabilizer, 1% of lubricant and 6% of toughening agent, adding the mixture into a double-screw extruder (the processing temperature is 100-240 ℃, the processing temperature is a conventional process in the field), and granulating the mixture after melt extrusion and cooling of the double-screw extruder to obtain 10% of short basalt fiber reinforced halogen-free flame-retardant PBT material (the fiber length is 0.1-0.6 mm, and the particle length is 3 mm). The percentage contents are all weight percentages. The starting materials were the same as in example 5.
Comparative example 3
The production method comprises the following steps of uniformly mixing raw materials with the PBT content of 48%, the halogen-free flame retardant content of 6%, the flame-retardant synergist content of 4%, the toughening agent content of 1%, the heat stabilizer content of 0.5% and the lubricant content of 0.5%, adding the raw materials into a double-screw extruder (the processing temperature is 100-240 ℃, the processing temperature is the conventional process in the field), carrying out melt extrusion on the raw materials into an impregnation die (the die temperature is 250 ℃), drawing out the basalt fiber (the content of 40%) from an impregnation die head, cooling, drawing and carrying out grain cutting to obtain 40% long basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material (the length of fibers and particles is equal to 11mm), and observing and recording the production manufacturability. The percentage contents are all weight percentages. The raw materials were the same as in example 2.
Comparative example 4
The production method comprises the following steps of uniformly mixing raw materials with the PBT content of 39.85%, the halogen-free flame retardant content of 5.1%, the flame-retardant synergist content of 3.4%, the toughening agent content of 0.85%, the heat stabilizer content of 0.5% and the lubricant content of 0.5%, adding the raw materials into a double-screw extruder (the processing temperature is 100-240 ℃, the processing temperature is a conventional process in the field), carrying out melt extrusion on the raw materials into an impregnation die, drawing out basalt fibers (the content is 49.8%) from an impregnation die head, cooling, drawing and carrying out grain cutting to obtain 49.8% long basalt fiber reinforced halogen-free flame-retardant polybutylene terephthalate material (the fibers and the particles are as long as 11mm), and observing and recording the production manufacturability. The percentage contents are all weight percentages. The raw materials were the same as in example 3.
The polybutylene terephthalate materials of the examples and comparative examples were subjected to the following performance tests (test results are shown in table 1):
(1) the mechanical test items are carried out according to ISO standards, namely tensile strength ISO 527-2, speed of 5mm/min, bending strength and bending modulus ISO 178, speed of 2mm/min, notch impact strength ISO 179/1eA and temperature of 23 ℃; (2) flame retardant property UL94, thickness 1.6 mm.
(3) The manufacturability is judged by taking the production continuity as a reference, and according to the production continuity problem caused by strip breakage in the production process, the manufacturability is sequentially judged to be poor, good and good (poor: strip breakage occurs after 30min of production, poor: strip breakage occurs after 1h of production, good: strip breakage occurs after 1-6 h of production, and good: strip breakage occurs after more than 6h of continuous production, and even uninterrupted production can be realized.
(4) Production efficiency is based on the number of finished products capable of being produced in unit time, and for the flame retardant material with specific fiber content directly produced by one-step method, high-speed production cannot be brought due to fiber dispersion in long fiber production, but under the same equipment, high-content long basalt fiber master batch is produced, and then is mixed with the flame retardant toughening master batch, so that the number of finished products is increased in proportion, and the production efficiency is high: yield over 800kg per hour, low: the output is 200-800 kg per hour, and is very low: the output per hour is less than 200 kg.
TABLE 1
Figure BDA0002801791330000101
Figure BDA0002801791330000111
As can be seen from Table 1, the test results of example 1 and example 5 are compared with those of comparative example 1 and comparative example 2, respectively, and the conventional short basalt fiber reinforced halogen-free flame retardant PBT material has low performance, especially low impact performance. The long basalt fiber reinforced halogen-free flame-retardant PBT material has excellent mechanical properties, particularly the impact property is obviously improved, 30% of basalt fiber with the same formula is compared with the short basalt material reinforced halogen-free flame-retardant PBT material, the notch impact property of the long basalt material reinforced halogen-free flame-retardant PBT material is improved by 126%, and 10% of basalt fiber with the same formula is compared with the short basalt material reinforced halogen-free flame-retardant PBT material, the notch impact property of the long basalt material reinforced halogen-free flame-retardant PBT material is improved by 124%.
The test results of example 2 and example 3 are compared with those of comparative example 3 and comparative example 4, respectively, and the test performance of the injection molded sample strip is relatively low due to the adoption of the methods of comparative example 3 and comparative example 4, which have poor production manufacturability, low production efficiency and relatively poor impregnation effect of the material.

Claims (10)

1. The high-impact-resistance long basalt fiber reinforced halogen-free flame-retardant PBT material is characterized in that the material is formed by blending long-fiber basalt fiber reinforced PBT master batch and halogen-free flame-retardant toughening master batch;
the long-fiber basalt fiber reinforced PBT master batch comprises the following components in percentage by weight: 20 to 60 percent of long basalt fiber, 38 to 79.6 percent of PBT resin, 0.2 to 1 percent of heat stabilizer and 0.2 to 1 percent of lubricant;
the halogen-free flame-retardant toughening master batch comprises the following components in percentage by weight: 14.6 to 92 percent of PBT resin, 5 to 50 percent of halogen-free flame retardant, 1 to 20 percent of flame retardant synergist, 0 to 15 percent of toughening agent, 0.2 to 1 percent of heat stabilizer and 0.2 to 1 percent of lubricant.
2. The material according to claim 1, wherein the PBT material has a percentage by weight of long basalt fibres of between 5% and 50%.
3. The material of claim 1, wherein the melt mass flow rate of the PBT resin in the PBT masterbatch is 20g/10min-100g/10 min.
4. The material of claim 1, wherein the melt mass flow rate of the PBT resin in the halogen-free flame retardant toughening master batch is 5g/10min-100g/10 min.
5. The material of claim 1, wherein the halogen-free flame retardant is at least one of melamine phosphate, red phosphorus, pentaerythritol phosphate, and hypophosphite; the flame-retardant synergist is at least one of zinc borate, titanium dioxide and hydrotalcite.
6. The material of claim 1, wherein the toughening agent is at least one of an ethylene-butyl acrylate-glycidyl methacrylate copolymer, a copolymer of ethylene and methyl acrylate.
7. The material of claim 1, wherein the thermal stabilizer is at least one of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, pentaerythritol tetrakis (3-laurylthiopropionate), tris [2, 4-di-tert-butylphenyl ] phosphite; the lubricant is at least one of ethylene bis stearamide, E wax, calcium stearate and pentaerythritol tetrastearate.
8. A process for the preparation of a PBT material of claim 1, comprising the steps of:
(1) adding PBT resin, a heat stabilizer and a lubricant into an extruder, melting and uniformly mixing, extruding into an impregnation die head, impregnating long basalt fiber in the impregnation die head, pulling out, and sequentially cooling, drawing and granulating to obtain long fiber basalt fiber reinforced PBT master batch;
(2) adding PBT resin, a halogen-free flame retardant, a flame-retardant synergist, a toughening agent, a heat stabilizer and a lubricant into a double-screw extruder to be melted and uniformly mixed, and then extruding and granulating to obtain halogen-free flame-retardant toughening master batches;
(3) and (2) uniformly mixing the long-fiber basalt fiber reinforced PBT master batch and the halogen-free flame retardant toughening master batch in the step (1) to obtain the high-impact-resistance long basalt fiber reinforced halogen-free flame retardant PBT material.
9. The method according to claim 8, wherein the length of the long fiber basalt fiber-reinforced PBT master batch in the step (1) is 3mm to 25 mm.
10. Use of the material according to claim 1 in the automotive, household electrical and tool fields.
CN202011352789.9A 2020-11-26 2020-11-26 High-impact-length basalt fiber reinforced halogen-free flame-retardant PBT material and preparation method thereof Pending CN112480610A (en)

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