CN103254614A - Bismaleimide modified thermoplastics and preparation method thereof - Google Patents
Bismaleimide modified thermoplastics and preparation method thereof Download PDFInfo
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- CN103254614A CN103254614A CN2012100357096A CN201210035709A CN103254614A CN 103254614 A CN103254614 A CN 103254614A CN 2012100357096 A CN2012100357096 A CN 2012100357096A CN 201210035709 A CN201210035709 A CN 201210035709A CN 103254614 A CN103254614 A CN 103254614A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention belongs to the technical field of modified plastics, and relates to a modified thermoplastics and a preparation method thereof. The modified thermoplastics is prepared by the following components by weight parts: 100 parts of the thermoplastic, 0.5-15 parts of the bimaleimide, 0-100 parts of glass fibre, 0-10 parts of a compatilizer and 0-50 parts of an auxiliary agent. Compared with prior art, the product provided by the invention not only improves antifriction performance and hardness of base plastic, but also provides a method for other materials to improve the antifriction performance and the hardness.
Description
Technical field
The invention belongs to the modified plastics technical field, relate to a kind of modified thermoplastic and preparation method thereof.
Background technology
Bismaleimides (BMI) is the compound that a class has the dual-active end group, has multiple premium propertiess such as high temperature resistant, radiation hardness, moisture-proof heat.Thermoplastics refers to have thermoplastic, the plastics of hardening by cooling characteristic, all has a wide range of applications at industry-by-industry.
Chinese patent 200510134995.1 discloses a kind of high-wearing polytetrafluoroethylcomposite composite material and preparation method thereof, and this method products obtained therefrom rub resistance resistance to elevated temperatures is good, and shortcoming is that cost is too high, the technology more complicated.Chinese patent 200810207474.8 discloses a kind of high wear-resisting glass fiber reinforced nylon composition and preparation method thereof, and this method products obtained therefrom crocking resistance is good, and mechanical property excellence, shortcoming are that the glass loading level is too high, product shrinking percentage height, and surface irregularity.
Summary of the invention
In order to overcome the defective of prior art, the object of the present invention is to provide a kind of bi-maleimide modified thermoplastics and preparation method thereof.The present invention is by adding bismaleimides in thermoplastics, can obtain that crocking resistance is good, smooth surface, shrinking percentage is low, mechanical property is good thermoplastics.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of modified thermoplastic, made by the component that comprises following weight part:
100 parts of thermoplasticss,
Bismaleimides 0.5-15 part,
Glass fibre 0-100 part,
Compatilizer 0-10 part,
Auxiliary agent 0-50 part.
The preferred 20-80 part of described glass fibre.
The preferred 3-10 part of described compatilizer.
The preferred 3-50 part of described auxiliary agent.
Described thermoplastics is selected from one or more in polymeric amide, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymeric amide, polyethylene terephthalate, polybutylene terephthalate or the acrylonitrile-butadiene-styrene copolymer.
Described bismaleimides is selected from diphenyl methane dimaleimide.
Described glass fibre is alkali free glass fibre.
Described compatilizer is selected from one or more in maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene, maleic anhydride graft polyvinyl chloride, maleic anhydride graft polystyrene, maleic anhydride graft acrylonitrile-butadiene-styrene copolymer, acrylic acid-grafted polypropylene, acrylic acid-grafted polyethylene or maleic anhydride grafted ethene-octene copolymer elastomerics.
Described auxiliary agent is selected from one or more in oxidation inhibitor, lubricant, fire retardant or the tinting material.
Described oxidation inhibitor is selected from three (2.4-di-tert-butyl-phenyl) phosphorous acid ester or four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
Described lubricant is selected from white oil, N, N-ethylenebisstearamide, solid paraffin or methyl-silicone oil.
Described fire retardant is selected from magnesium hydroxide, antimonous oxide, aluminium hydroxide or molybdenum oxide.
Described tinting material is selected from titanium dioxide, lithopone, chrome yellow, cadmium red or ultramarine.
A kind of preparation method of above-mentioned modified thermoplastic, this method may further comprise the steps:
(1) takes by weighing each component raw material by said ratio, take by weighing 100 parts of thermoplasticss, 0.5-15 part bismaleimides, 0-10 part compatilizer and 0-50 part auxiliary agent, high mixer mixing 1-5 minute;
(2) mixture that then step (1) is made joins in the twin screw extruder, with the mixing extruding pelletization of 0-100 part glass fibre, prepares bi-maleimide modified thermoplastics under 130-255 ℃.
Beneficial effect of the present invention:
Compared with prior art, products obtained therefrom of the present invention has not only improved crocking resistance and the hardness of matrix plastic, and provides a kind of method to other materials raising rub resistance and hardness.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
The batten of making is carried out friction-wear test, and concrete parameter is as follows:
Friction wear testing machine model: MM-200; Lubricating condition: metal to-metal contact; Envrionment conditions: 6 ℃;
Test pressure: 150N; Test period: 90min; Following sample material: 45# steel; Following sample rotating speed: 200r/min.
Some used among embodiment starting material see Table 1.
Table 1
Embodiment 1
Take by weighing the PP of 100 parts of S2040,0.5 part of BMI, 168,0.02 parts of lubricant 36# of 1018,0.02 parts of oxidation inhibitor of 0.02 part of oxidation inhibitor white oil mixed 1 minute in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 180 ℃ in I district, 190 ℃ in II district, 195 ℃ in III district, 200 ℃ in IV district, 205 ℃ in V district, 210 ℃ in VI district, 215 ℃ of heads, after material is extruded, through water-cooled, pelletizing, pellet was 100 ℃ of following forced air dryings 3 hours, make batten by injection moulding machine, place after 16 hours under 25 ℃ of constant temperature and test, hardness and frictional behaviour test result see Table 2.
Embodiment 2
Take by weighing the PP of 100 parts of S2040,7 parts of BMI, 168,0.02 parts of lubricant 36# of 1018,0.02 parts of oxidation inhibitor of 0.02 part of oxidation inhibitor white oil mixed 3 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 180 ℃ in I district, 190 ℃ in II district, 195 ℃ in III district, 200 ℃ in IV district, 205 ℃ in V district, 210 ℃ in VI district, 215 ℃ of heads, after material is extruded, through water-cooled, pelletizing, pellet was 100 ℃ of following forced air dryings 3 hours, make batten by injection moulding machine, place after 16 hours under 25 ℃ of constant temperature and test, hardness and frictional behaviour test result see Table 2.
Embodiment 3
Take by weighing the PP of 100 parts of S2040,15 parts of BMI, 168,0.02 parts of lubricant 36# of 1018,0.02 parts of oxidation inhibitor of 0.02 part of oxidation inhibitor white oil mixed 5 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 180 ℃ in I district, 190 ℃ in II district, 195 ℃ in III district, 200 ℃ in IV district, 205 ℃ in V district, 210 ℃ in VI district, 215 ℃ of heads, after material is extruded, through water-cooled, pelletizing, pellet was 100 ℃ of following forced air dryings 3 hours, make batten by injection moulding machine, place after 16 hours under 25 ℃ of constant temperature and test, hardness and frictional behaviour test result see Table 2.
Comparative Examples 1
Take by weighing the PP of 100 parts of S2040,168,0.02 parts of lubricant 36# of 1018,0.02 parts of oxidation inhibitor of 0.02 part of oxidation inhibitor white oil mixed 3 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 180 ℃ in I district, 190 ℃ in II district, 195 ℃ in III district, 200 ℃ in IV district, 205 ℃ in V district, 210 ℃ in VI district, 215 ℃ of heads, after material is extruded, through water-cooled, pelletizing, pellet was 100 ℃ of following forced air dryings 3 hours, make batten by injection moulding machine, place after 16 hours under 25 ℃ of constant temperature and test, hardness and frictional behaviour test result see Table 2.
Table 2 The performance test results
Comparative Examples 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
Rockwell hardness (R) | 87.5 | 89.3 | 95.7 | 101 |
Tensile strength (MPa) | 33.1 | 33.9 | 35.6 | 37.8 |
Flexural strength (MPa) | 44.1 | 45.3 | 46.1 | 47.5 |
Polishing scratch width (mm) | 14.81 | 12.35 | 6.23 | 4.31 |
As can be seen from Table 2, in PP, add tensile strength, flexural strength, Rockwell hardness and polishing scratch width that bismaleimides can improve PP, obtained that mechanical property is good, the MODIFIED PP of rub resistance.
Embodiment 4
Take by weighing 100 parts of PBT, 1 part of BMI, 0.02 part oxidation inhibitor 1018,0.02 part oxidation inhibitor 168,0.02 part lubricant N, the hard esteramides of N-ethylenebis, 0.02 part of tinting material titanium dioxide, in high-speed mixer, mixed 2 minutes, with the material that mixes with 50 parts of glass fibre extruding pelletization in twin screw extruder.
Extruder temperature is set to: 200 ℃ in I district, 220 ℃ in II district, 230 ℃ in III district, 240 ℃ in IV district, 245 ℃ in V district, 250 ℃ in VI district, 250 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 5
Take by weighing 100 parts of PBT, 2 parts of BMI, 0.02 part oxidation inhibitor 1018,0.02 part oxidation inhibitor 168,0.02 part lubricant 36# white oil, 10 parts of molybdenum oxides, 0.02 part of tinting material lithopone, in high-speed mixer, mixed 4 minutes, with the material that mixes with 100 parts of alkali free glass fibres extruding pelletization in twin screw extruder.
Extruder temperature is set to: 200 ℃ in I district, 220 ℃ in II district, 230 ℃ in III district, 240 ℃ in IV district, 245 ℃ in V district, 250 ℃ in VI district, 250 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 6
Take by weighing the PA6 of 100 parts of M2500,3 parts of BMI, 10 parts of compatilizer POE-g-MAH, 0.03 part antioxidant 1010,0.01 part oxidation inhibitor 168 mixed 3 minutes in high-speed mixer, with the material that mixes with 20 parts of glass fibre extruding pelletization in twin screw extruder.
Extruder temperature is set to: 200 ℃ in I district, 220 ℃ in II district, 235 ℃ in III district, 240 ℃ in IV district, 235 ℃ in V district, 235 ℃ in VI district, 240 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 7
Take by weighing the PA6 of 100 parts of M2500,4 parts of BMI, 5 parts of compatilizer POE-g-MAH, 25 parts of fire retardant magnesium hydroxides, 0.03 part antioxidant 1010,168,0.06 parts of solid paraffins of 0.01 part of oxidation inhibitor, in high-speed mixer, mixed 3 minutes, with the material that mixes with 10 parts of glass fibre extruding pelletization in twin screw extruder.
Extruder temperature is set to: 200 ℃ in I district, 220 ℃ in II district, 235 ℃ in III district, 240 ℃ in IV district, 235 ℃ in V district, 235 ℃ in VI district, 240 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 8
Take by weighing the PA6 of 100 parts of M2500,5 parts of BMI, 50 parts of fire retardant magnesium hydroxides mixed in high-speed mixer 3 minutes, with the material that mixes with 10 parts of glass fibre extruding pelletization in twin screw extruder.
Extruder temperature is set to: 200 ℃ in I district, 220 ℃ in II district, 235 ℃ in III district, 240 ℃ in IV district, 235 ℃ in V district, 235 ℃ in VI district, 240 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 9
Take by weighing 100 parts of ABS, 6 parts of BMI, 0.02 part of oxidation inhibitor 1018,0.02 part 168,0.02 parts of lubricant methyl-silicone oils of oxidation inhibitor, 0.02 part of cadmium red, in high-speed mixer, mixed 3 minutes, with the material that mixes with 30 parts of glass fibre extruding pelletization in twin screw extruder.
Extruder temperature is set to: 180 ℃ in I district, 185 ℃ in II district, 190 ℃ in III district, 195 ℃ in IV district, 200 ℃ in V district, 205 ℃ in VI district, 210 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 10
Take by weighing 100 parts of PS, 8 parts of BMI, 7 parts of PS-g-MAH, 0.02 part 168,0.02 parts of lubricant 36# of 1018,0.02 parts of oxidation inhibitor of oxidation inhibitor white oil, in high-speed mixer, mixed 3 minutes, with the material that mixes with 40 parts of glass fibre extruding pelletization in twin screw extruder.
Extruder temperature is set to: 180 ℃ in I district, 185 ℃ in II district, 190 ℃ in III district, 195 ℃ in IV district, 200 ℃ in V district, 205 ℃ in VI district, 210 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 11
Take by weighing 100 parts of PET, 11 parts of BMI, 168,0.01 parts of lubricant 36# of 1018,0.01 parts of oxidation inhibitor of 0.01 part of oxidation inhibitor white oil mixed in high-speed mixer 2 minutes, with the material that mixes with 25 parts of glass fibre extruding pelletization in twin screw extruder.
Extruder temperature is set to: 220 ℃ in I district, 230 ℃ in II district, 235 ℃ in III district, 250 ℃ in IV district, 250 ℃ in V district, 250 ℃ in VI district, 255 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 12
Take by weighing 100 parts of PVC, 13 parts of BMI, 1018,0.02 parts of lubricant 36# of 0.02 part of oxidation inhibitor white oil mixed 2 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 130 ℃ in I district, 150 ℃ in II district, 160 ℃ in III district, 170 ℃ in IV district, 175 ℃ in V district, 180 ℃ in VI district, 185 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 13
Take by weighing 100 parts of PE, 15 parts of BMI, 168,0.02 parts of lubricant 36# of 0.03 part of oxidation inhibitor white oil, 3 parts of tinting material cadmium reds were mixed 2 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 150 ℃ in I district, 160 ℃ in II district, 170 ℃ in III district, 175 ℃ in IV district, 180 ℃ in V district, 185 ℃ in VI district, 185 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 14
Take by weighing 100 parts of PE, 7.5 parts of BMI, 10 parts of antimonous oxides mixed 2 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 150 ℃ in I district, 160 ℃ in II district, 170 ℃ in III district, 175 ℃ in IV district, 180 ℃ in V district, 185 ℃ in VI district, 185 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 15
Take by weighing 100 parts of PE, 7.5 parts of BMI, 10 parts of antimonous oxides, 40 parts of magnesium hydroxides mixed 2 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 150 ℃ in I district, 160 ℃ in II district, 170 ℃ in III district, 175 ℃ in IV district, 180 ℃ in V district, 185 ℃ in VI district, 185 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
Embodiment 16
Take by weighing 100 parts of PE, 15 parts of BMI mixed 2 minutes in high-speed mixer, with the material extruding pelletization in twin screw extruder that mixes.
Extruder temperature is set to: 150 ℃ in I district, 160 ℃ in II district, 170 ℃ in III district, 175 ℃ in IV district, 180 ℃ in V district, 185 ℃ in VI district, 185 ℃ of heads after material is extruded, through water-cooled, pelletizing, namely obtain product of the present invention.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. modified thermoplastic is characterized in that: made by the component that comprises following weight part:
100 parts of thermoplasticss,
Bismaleimides 0.5-15 part,
Glass fibre 0-100 part,
Compatilizer 0-10 part,
Auxiliary agent 0-50 part.
2. modified thermoplastic according to claim 1, it is characterized in that: described glass fibre is 20-80 part;
Or described compatilizer is 3-10 part;
Or described auxiliary agent is 3-50 part.
3. modified thermoplastic according to claim 1, it is characterized in that: described thermoplastics is selected from one or more in polymeric amide, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymeric amide, polyethylene terephthalate, polybutylene terephthalate or the acrylonitrile-butadiene-styrene copolymer.
4. modified thermoplastic according to claim 1, it is characterized in that: described bismaleimides is selected from diphenyl methane dimaleimide.
5. modified thermoplastic according to claim 1, it is characterized in that: described glass fibre is alkali free glass fibre.
6. modified thermoplastic according to claim 1, it is characterized in that: described compatilizer is selected from one or more in maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene, maleic anhydride graft polyvinyl chloride, maleic anhydride graft polystyrene, maleic anhydride graft acrylonitrile-butadiene-styrene copolymer, acrylic acid-grafted polypropylene, acrylic acid-grafted polyethylene or maleic anhydride grafted ethene-octene copolymer elastomerics.
7. modified thermoplastic according to claim 1, it is characterized in that: described auxiliary agent is selected from one or more in oxidation inhibitor, lubricant, fire retardant or the tinting material.
8. modified thermoplastic according to claim 7, it is characterized in that: described oxidation inhibitor is selected from three (2.4-di-tert-butyl-phenyl) phosphorous acid ester or four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester;
Or described lubricant is selected from white oil, N, N-ethylenebisstearamide, solid paraffin or methyl-silicone oil.
9. modified thermoplastic according to claim 7, it is characterized in that: described fire retardant is selected from magnesium hydroxide, antimonous oxide, aluminium hydroxide or molybdenum oxide;
Or described tinting material is selected from titanium dioxide, lithopone, chrome yellow, cadmium red or ultramarine.
10. the preparation method of arbitrary described modified thermoplastic among the claim 1-9, it is characterized in that: this method may further comprise the steps:
(1) takes by weighing each component raw material by the described proportioning of claim 1, take by weighing 100 parts of thermoplasticss, 0.5-15 part bismaleimides, 0-10 part compatilizer and 0-50 part auxiliary agent, high mixer mixing 1-5 minute;
(2) mixture that then step (1) is made joins in the twin screw extruder, with the mixing extruding pelletization of 0-100 part glass fibre, prepares bi-maleimide modified thermoplastics under 130-255 ℃.
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