CN101260226A - Method for preparing high machinery performance halogen-free anti-flaming PBT composite and composite material - Google Patents
Method for preparing high machinery performance halogen-free anti-flaming PBT composite and composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of high-mechanical property halogen-free fire-retarding PBT composite material. The preparation method comprises the following steps: (1) weighing, (2) mixing and (3) mixing milling and extrusion. The invention also discloses a composite material prepared through adopting the method. The composite material comprises the following components: PBT, ultrafine glass fiber, hindered phenol antioxidant, organic phosphorous acid ester, toughening agent, fire retardant A, fire retardant B and lubricant. The composite material has the advantages that: the fire-retarding performance of the composite material reaches to UL94V-0(0.8mm) grade, and the composite material has more outstanding mechanical property than the prior halogen-free fire-retarding system; meanwhile, because the mechanical property is equivalent to that of a halogen-containing fire-retarding system, the composite material can completely replace the prior halogen-containing fire-retarding product and halogen-free fire-retarding product; moreover, the composite material, which has simple preparation method and is easy to operate, can be widely used in household appliance spare parts and electronic product accessories, etc, and particularly in cooling fans in the IT industry.
Description
Technical field
The present invention relates to polymer composite and preparation method thereof, be specifically related to a kind of preparation method and matrix material of halogen-free anti-flaming PBT composite of the high-mechanical property that can be used for industries such as the various household appliances that the environmental protection flame retardant requirement arranged of injection moulding, electronic product accessory.
Background technology
In the prior art, make the fire retardant that anti-flaming PBT composite adopted, about 95% is halogen containing flame-retardant, be the brominated flame-retardant of representative with polybromodiphenyl ether and polybrominated biphenyl material particularly, its efficient height, consumption are few, and be little to the performance impact of material, and it is moderate, its usefulness/price can be equal to than non-other fire retardants, so in China's electronic apparatus series products for export, about 70～80% have all adopted the matrix material that contains this based flame retardant.But in recent years, because bromide fire retardant is subjected to the puzzlement of Dioxins problem, use its (bromo-antimony system) fire-retardant polymer composite the time can generate a large amount of flue dust and corrosive gases in thermo-cracking and burning simultaneously, European Union and Japan put into effect in succession that it is forbidden by decree to this based flame retardant of use are produced matrix material at present.European Union has risen on July 1st, 2006 and has implemented in full the ROHS instruction, and the electronic and electrical equipment that this decree requires to throw in European Union must not contain components such as polybromodiphenyl ether, Polybrominated biphenyl; Japan has also put into effect corresponding standard JISC0950, and the SONY-SS-00259 standard that Sony Corporation puts into effect is more strict to the requirement of fire retardant; In the U.S., the use of bromide fire retardant is forbidden in the legislation of indivedual state government.Therefore, above decree and standard have had a strong impact on the outlet that China adopts the electronic and electrical equipment that the matrix material of this component produces, and therefore must greatly develop the development trend that bittern-free flame-proof material could adapt to the world market.In order to promote quality product, cooperate the requirement of international standard, " the electronics and IT products pollution control management way " of Chinese version RoHS is also from formal enforcement on March 1 in 2007.Also occurred bittern-free flame-proof material in the prior art, this fire retardant material can satisfy environmental protection requirement substantially, but problem such as this series products ubiquity manufacturing course complexity, product mechanical property be lower is applied it and is subjected to certain restriction.Therefore study manufacture method of a kind of high machinery performance halogen-free anti-flaming material and products thereof, promptly become present problem demanding prompt solution.
Summary of the invention
The technical problem to be solved in the present invention is, the low problem of bittern-free flame-proof material mechanical property of producing at preparation method of the prior art, but a kind of preparation method of industrialized mass production high machinery performance halogen-free anti-flaming PBT composite is provided.
Second technical problem that the present invention will solve is, at the lower problem of bittern-free flame-proof material mechanical property of the prior art, the high machinery performance halogen-free anti-flaming PBT composite that adopts preceding method to produce is provided, this matrix material is the flame retardant properties excellence not only, and environmental protection, safety, electrical insulation capability excellence.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of preparation method of high machinery performance halogen-free anti-flaming PBT composite is characterized in that, may further comprise the steps:
(1) weighing: take by weighing each feed composition: PBT, beta glass fibre, hindered phenol antioxygen, organophosphite, toughner, fire retardant A, fire retardant B, lubricant respectively according to prescription;
(2) mix: each component is added in the agitation vat in proportion, stir and make its thorough mixing;
(3) mixing extruding: the raw material behind the thorough mixing is added in the forcing machine, carry out twice above melting mixing after, extrude granulation.
Described step (1) is further comprising the steps of:
(11) preparation fire retardant B: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, it is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places N
2Atmosphere in, it is carried out pyroprocessing, all be cooled to room temperature repeatedly more than twice or twice, and after finishing pyroprocessing each time;
(c) silane coupling agent is watered on the cooled hypophosphite surface, after stirring fully absorbs it, make fire retardant B.
Described step (1) is further comprising the steps of:
(12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively,, stir then with the two mixing.
Described step (11) and (12) no sequencing.
Described step (3), be that the raw material behind the thorough mixing is added in the twin screw extruder, carry out melting mixing, extrude and granulation that the screw diameter of this twin screw extruder is 30～90mm, the ratio of spiro rod length and diameter is set at 36～40, and extrusion temperature is 200～260 ℃.
Step of the present invention (11), owing to having superior especially consistency between the fire retardant B for preparing through surface treatment step and other components in the matrix material, greatly improved interface between each component in conjunction with dynamics, the lifting of the matrix material machinery performance of preparation is had crucial effects.
Step of the present invention (12) before each component being carried out step (2) mixing, with alkali free glass fibre and silane mixture, stirs, and is prepared into surface treated alkali free glass fibre.Other component compatibilities in surface treated glass fibre and the matrix material are stronger, help further strengthening the mechanical property of whole matrix material.
A kind of matrix material that adopts aforementioned high machinery performance halogen-free anti-flaming PBT composite preparation method is characterized in that, it comprises the component of following weight part ratio:
PBT 35～70％；
Beta glass fibre 0～40%;
Hindered phenol antioxygen 0.2～0.5%;
Organophosphite 0.2～0.5%;
Toughner 0.5～5%;
Fire retardant A 5～10%;
Fire retardant B 15～25%;
Lubricant 0.3～1%.
Wherein said hindered phenol antioxygen is four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol ester; Wherein said organophosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; Wherein said toughner is the multipolymer of methyl methacrylate and butyl acrylate; Wherein said fire retardant A is a melamine phosphate, and described fire retardant B is the mixture of surface treated hypophosphite and silane; Wherein said lubricant is a montanin wax; This montanin wax is brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester and lipid acid-montanin wax calcium salt.
Wherein, described beta glass fibre can well merge with the PBT in the component through surface treatment, has improved the mechanical property of material effectively; Described hindered phenol antioxygen is a primary antioxidant, and described hindered phenol antioxygen is specially four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol ester; Described organophosphite is an auxiliary antioxidant, and described organophosphite is specially three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Among the present invention, the adding of oxidation inhibitor can make PBT have good processing stability in the course of processing, avoids color and luster, performance to change.
Wherein, the methyl methacrylate that toughner comprised and the multipolymer of butyl acrylate can well merge with described PBT body material, have strengthened the toughness of matrix material, can promote the mechanical property of material.
Fire retardant A wherein is a melamine phosphate, and fire retardant B is the mixture of surface treated hypophosphite and silane.Hypophosphite and silane will carry out surface treatment before compound, the fire retardant B mixture of Xing Chenging and other components in the composition (especially PBT that content is bigger and beta glass fibre) have better consistency like this, greatly improved interface between each component in conjunction with dynamics, not only effectively raise the flame retardant resistance of whole material, flame retardant rating reaches UL 94 V-0 levels (0.8mm), improve the mechanical property of this material more greatly, effectively solved the low relatively difficult problem of bittern-free flame-proof material mechanical property of the prior art.
Lubricant wherein can promote the fusion of each component, improves the flowability of described matrix material molten mass effectively, reduces the friction between matrix material solution and processor in the course of processing, has good demoulding effect simultaneously, shortens injection cycle.
Beneficial effect of the present invention is: the preparation method of high machinery performance halogen-free anti-flaming PBT composite provided by the present invention, the technology that it is traditional relatively, it has increased the step of in advance the part component being handled, adopt the halogen-free anti-flaming PBT composite mechanical property height of this method preparation, flame retardant properties is good, the lifting of composite property is had decisive action, and preparation technology is simple, operation easily, the constant product quality of preparation.Matrix material provided by the invention, with respect to halogen-free flameproof product of the prior art, not only its flame retardant properties reaches UL 94 V-0 (0.8mm) level, and has more outstanding mechanical property than existing halogen-free flame-retardant system, suitable with the mechanical property of Halogen flame-retardant system, therefore can substitute the matrix material of the fire-retardant and halogen-free flameproof of existing Halogen fully.The present invention can be widely used in the manufacturing of matrix materials such as household electrical appliances accessory, electronic product accessory or product, is specially adapted to make the used radiator fan of IT industry.
Below in conjunction with embodiment, the present invention is described in more detail.
Embodiment
Embodiment 1: a kind of preparation method of high machinery performance halogen-free anti-flaming PBT composite may further comprise the steps:
(1) weighing:, take by weighing each feed composition: PBT, beta glass fibre, hindered phenol antioxygen, organophosphite, toughner, fire retardant A, fire retardant B, lubricant respectively according to wherein filling a prescription referring to table 1;
(11) preparation fire retardant B: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, hypophosphite is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places N
2Atmosphere in, it is carried out pyroprocessing, all be cooled to room temperature repeatedly more than twice or twice, and after finishing pyroprocessing each time;
(c) silane coupling agent is watered on the cooled hypophosphite surface, after stirring fully absorbs it, make fire retardant B.
(12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively,, stir then with the two mixing.This step (11) and (12) no sequencing.
(2) mix: each component is added in the agitation vat in proportion, stir and make its thorough mixing;
(3) mixing extruding: the raw material behind the thorough mixing is added in the forcing machine, carry out twice above melting mixing after, extrude granulation.In the present embodiment, be that the raw material behind the thorough mixing is added in the twin screw extruder, carry out melting mixing, extrude and granulation; The screw diameter of this twin screw extruder is 30～90mm, and the ratio of spiro rod length and diameter is set at 36～40, and extrusion temperature is 200～260 ℃.
Referring to table 1, a kind of matrix material that adopts aforementioned high machinery performance halogen-free anti-flaming PBT composite preparation method, it comprises following weight part ratio component: PBT 35～70%, beta glass fibre 0～40%; Hindered phenol antioxygen 0.2～0.5%; Organophosphite 0.2～0.5%; Toughner 0.5～5%; Fire retardant A 5～10%; Fire retardant B 15～25%; Lubricant 0.3～1%.
Concrete, in the present embodiment, the CAS NO. of described PBT is 26062-94-2; Described beta glass fibre (CAS NO. is 65997-17-3) is a toughener, and this glass fibre carries out surface treatment with silane, can well merge with the PBT in the component; Described hindered phenol antioxygen is a primary antioxidant, is specially four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol esters (CAS NO. is 6683-19-8); Described toughner is the multipolymer (CAS NO. is 25852-37-3) of methyl methacrylate and butyl acrylate; Described auxiliary antioxidant adopts organophosphite, is specially three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (CAS NO. is 31570-04-4); Described fire retardant A is melamine phosphate (CAS NO. is 218768-84-4); Described fire retardant B is the mixture of hypophosphite (CAS NO. is 6303-21-5) and silane; Described lubricant is a montanin wax, is specially brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester (CAS NO. is 73138-44-0) and lipid acid-montanin wax calcium salt (CAS NO. is 68308-22-5).
Preparation method concrete in the present embodiment is: take by weighing each raw material successively in each the ingredients weight parts ratio shown in table 1 the 2nd row; Before mixing, wherein hypophosphite is carried out surface treatment, detailed process is: at first hypophosphite is ground 1～10h, oven dry then places N with the hypophosphite after the oven dry
2Atmosphere in, repeated multiple times (minimum should being generally 3～6 times more than twice) is carried out pyroprocessing, makes its surface state that once chapped, and silane is watered on the hypophosphite surface after being cooled to room temperature, mixes to stir that it is fully absorbed, and promptly makes fire retardant B; Surface treatment process before alkali free glass fibre mixes is: with alkali free glass fibre and silane mixture, stir, make its abundant, uniform mixing.The two also can carry out simultaneously.
Each component is reached fire retardant B, the alkali free glass fibre for preparing in advance, get in proportion material add stir thorough mixing in the agitation vat after, add again and carry out repeated multiple times in the twin screw extruder (more than twice, be generally 3～6 times) melting mixing, make each component react fusion fully after, extrude, granulation, the screw diameter of twin screw extruder is 30mm, and the ratio of spiro rod length and diameter is set at 36, and extrusion temperature is 200 ℃.
Embodiment 2: the preparation method of the high machinery performance halogen-free anti-flaming PBT composite that present embodiment provides and matrix material, it is identical with embodiment 1 basically, its difference is, the screw diameter of twin screw extruder is 90mm, the ratio of spiro rod length and diameter is set at 40, and extrusion temperature is 260 ℃; The raw material that this matrix material comprises is table 1 the 3rd listed component of row and part by weight.
Embodiment 3: the preparation method of a kind of high machinery performance halogen-free anti-flaming PBT composite that present embodiment provides and matrix material, basically identical with embodiment 1, its difference is, the screw diameter of twin screw extruder is 60mm, the ratio of spiro rod length and diameter is set at 38, and extrusion temperature is 230 ℃; The raw material that this matrix material comprises is table 1 the 4th listed component of row and part by weight.
Table 1
| Material name | Embodiment 1 (wt%) | Embodiment 2 (wt%) | Embodiment 3 (wt%) |
| Polybutylene terepthatlate | 37.5 | 53.7 | 62.6 |
| Beta glass fibre | 33 | 15 | 5 |
| Hindered phenol antioxygen | 0.2 | 0.4 | 0.5 |
| Organophosphite | 0.3 | 0.2 | 0.5 |
| Fire retardant A: melamine phosphate | 9 | 7 | 5 |
| Fire retardant B: the mixture of hypophosphite and silane | 15 | 20 | 25 |
| The multipolymer of methyl methacrylate and butyl acrylate | 4 | 3 | 1 |
| Montanin wax | 1 | 0.7 | 0.4 |
The prepared high machinery performance halogen-free anti-flaming PBT composite sample of above three embodiment is carried out test performance, its result and employing standard see Table 2, itself and the contrast of traditional bromo-antimony flame-retardant system test result are as can be known, the mechanical property of the matrix material that the present invention is prepared is compared with other halogen-free flame-retardant systems with flame retardant effect, not only each parameter of its mechanical property is higher than other halogen-free flame-retardant systems far away, and its flame retardant properties also reaches V-0 (0.8mm) grade, has excellent technique effect.Matrix material provided by the invention is compared with traditional bromo-antimony flame-retardant system, its mechanical property is suitable, and anti-electric arc ability is far above bromo-antimony flame-retardant system, so this composite property reaches the performance requirement to plastic material such as household electrical appliances accessory, electronic product accessory fully, has broad application prospects.
Table 2
| Test event | Testing standard | Embodiment 1 (containing 33% glass) | Embodiment 2 (containing 15% glass) | Embodiment 3 (containing 5% glass) | Bromo-antimony flame retardant products (containing 30% glass) | Halogen-free flameproof product (containing 32.9% glass) |
| Density (g/cm 3) | ISO1183 | 1.60 | 1.45 | 1.35 | 1.68 | |
| Vertical forming shrinking percentage (%) | LIXIN-EP | 0.4 | 0.6 | 1 | 0.4 | |
| Parallel molding shrinkage (%) | LIXIN-EP | 0.2 | 0.3 | 0.8 | 0.2 | |
| Tensile strength (Mpa) | ISO527 | 120 | 90 | 65 | 130 | 103 |
| Elongation at break (%) | ISO527 | 1.7 | 3 | 5 | 2.5 | 2 |
| Flexural strength | ISO178 | 170 | 135 | 95 | 180 | 148.4 |
| Modulus in flexure | ISO178 | 10500 | 8500 | 4500 | 10000 | 7380 |
| Notched Izod impact strength | ISO180 | 9.5 | 8 | 4.5 | 9.5 | 8.9 |
| Unnotched impact strength | ISO180 | 50 | 30 | 12 | 50 | |
| Fusing point | ISO3146-C | 220-225 | 220-225 | 220-225 | 220-225 | |
| Heat-drawn wire (66psi) | ISO75-1 | 220 | 210 | 200 | 220 | |
| Heat-drawn wire (264psi) | ISO75-2 | 210 | 200 | 140 | 210 | |
| 0.8mm flame retardant rating | ISO1210/UL9 4 | V-0 | V-0 | V-0 | V-0 | V-1 |
| 1.6mm glowing filament (℃) | IEC 695-2-1 | 960 | 960 | 960 | 960 | 960 |
| Anti-electric arc (Volt) | UL-746A | 600 | 525 | 500 | 325 | 550 |
Claims (10)
1. the preparation method of a high machinery performance halogen-free anti-flaming PBT composite is characterized in that, may further comprise the steps:
(1) weighing: take by weighing each feed composition: PBT, beta glass fibre, hindered phenol antioxygen, organophosphite, toughner, fire retardant A, fire retardant B, lubricant respectively according to prescription;
(2) mix: each component is added in the agitation vat in proportion, stir and make its thorough mixing;
(3) mixing extruding: the raw material behind the thorough mixing is added in the forcing machine, carry out twice above melting mixing after, extrude granulation.
2. the preparation method of high machinery performance halogen-free anti-flaming PBT composite according to claim 1 is characterized in that, described step (1) is further comprising the steps of:
(11) preparation fire retardant B: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, hypophosphite is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places the atmosphere of N2, and it is carried out pyroprocessing, all is cooled to room temperature repeatedly more than twice or twice, and after finishing pyroprocessing each time;
(c) silane coupling agent is watered on the cooled hypophosphite surface, after stirring fully absorbs it, make fire retardant B.
3. according to the preparation method of claim 1 or 2 described high machinery performance halogen-free anti-flaming PBT composites, it is characterized in that, described step (1) is further comprising the steps of: (12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively, with the two mixing, stir then.
Described step (11) and (12) no sequencing.
4. according to the preparation method of the described high machinery performance halogen-free anti-flaming PBT composite of claim 1, it is characterized in that described step (3) is that the raw material behind the thorough mixing is added in the twin screw extruder, carries out melting mixing, extrudes and granulation; The screw diameter of this twin screw extruder is 30～90mm, and the ratio of spiro rod length and diameter is set at 36～40, and extrusion temperature is 200～260 ℃.
5. a matrix material that adopts the described high machinery performance halogen-free anti-flaming PBT composite preparation method of claim 1 is characterized in that, it comprises the component of following weight part ratio:
PBT 35～70％；
Beta glass fibre 0～40%;
Hindered phenol antioxygen 0.2～0.5%;
Organophosphite 0.2～0.5%;
Toughner 0.5～5%;
Fire retardant A 5～10%;
Fire retardant B 15～25%;
Lubricant 0.3～1%.
6. matrix material according to claim 5 is characterized in that: wherein said hindered phenol antioxygen is four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol ester.
7. high machinery performance halogen-free anti-flaming PBT composite according to claim 5 is characterized in that: wherein said organophosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
8. matrix material according to claim 5 is characterized in that: wherein said toughner is the multipolymer of methyl methacrylate and butyl acrylate.
9. matrix material according to claim 5 is characterized in that: wherein said fire retardant A is a melamine phosphate, and described fire retardant B is the mixture of surface treated hypophosphite and silane.
10. matrix material according to claim 5 is characterized in that: wherein said lubricant is a montanin wax, and this montanin wax is brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester and lipid acid-montanin wax calcium salt.
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| CN105037879A (en) * | 2015-06-30 | 2015-11-11 | 成都硕屋科技有限公司 | Flame retardation master batch for polyolefin, and preparation method thereof |
| CN108659264A (en) * | 2018-04-19 | 2018-10-16 | 深圳市飞荣达科技股份有限公司 | Mixed type fire retardant for modified plastics and preparation method thereof, modified plastics |
| CN110819082A (en) * | 2019-09-30 | 2020-02-21 | 广东轻工职业技术学院 | High-weld-mark-strength glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN110819082B (en) * | 2019-09-30 | 2021-07-06 | 广东轻工职业技术学院 | High-weld-mark-strength glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN114106527A (en) * | 2021-12-28 | 2022-03-01 | 利尔化学股份有限公司 | Anti-dripping halogen-free flame-retardant PBT (polybutylene terephthalate) -based composite material and preparation method thereof |
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| CN114106527B (en) * | 2021-12-28 | 2023-11-28 | 利尔化学股份有限公司 | Anti-dripping halogen-free flame-retardant PBT-based composite material and preparation method thereof |
| CN114230985B (en) * | 2021-12-28 | 2024-04-09 | 上海普利特复合材料股份有限公司 | High-flame-retardance precipitation-resistant halogen-free flame-retardant reinforced PBT material and preparation method thereof |
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