CN115975366A - Modified polycarbonate resin, product and preparation method thereof - Google Patents
Modified polycarbonate resin, product and preparation method thereof Download PDFInfo
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- CN115975366A CN115975366A CN202310059817.5A CN202310059817A CN115975366A CN 115975366 A CN115975366 A CN 115975366A CN 202310059817 A CN202310059817 A CN 202310059817A CN 115975366 A CN115975366 A CN 115975366A
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 136
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title 1
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 85
- 239000004417 polycarbonate Substances 0.000 claims abstract description 85
- 239000000155 melt Substances 0.000 claims abstract description 44
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 239000011259 mixed solution Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000012989 trithiocarbonate Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 230000009286 beneficial effect Effects 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified polycarbonate resin, a product thereof and a preparation method thereof, and relates to the field of polycarbonate materials. Wherein the modified polycarbonate resin comprises 100 parts by weight of polycarbonate resin, 0.8-1.5 parts by weight of acrylonitrile-styrene-acrylate copolymer, 0.5-1.2 parts by weight of acrylonitrile-styrene-N-phenylmaleimide copolymer, 0.5-1 part by weight of antioxidant and 0.5-1 part by weight of uvioresistant agent; the melt index of the polycarbonate resin is 6-12g/10min; the melt index of the acrylonitrile-styrene-acrylate copolymer is 8-12g/10min; the acrylonitrile-styrene-N-phenylmaleimide copolymer has a melt index of 6-10g/10min. The hardness of the modified polycarbonate reaches 3H, and the high requirements in the fields of mobile phone shells, high-grade electrical appliance panels and the like are met.
Description
Technical Field
The invention relates to the field of polycarbonate materials, in particular to a modified polycarbonate resin, a product and a preparation method thereof.
Background
Polycarbonate is a material with good transparency, strong impact strength and thermal stability, and has wide application in various fields of national economy such as buildings, electronics, automobiles, medical treatment and the like.
However, the surface scratch resistance of the polycarbonate material is poor, so that the aesthetic degree of the product is greatly reduced, and when scratches are generated on the surface of the product, the stress concentration is easily caused by the scratches, so that the mechanical property of the polycarbonate material is reduced.
At present, the common scratch-resistant agent for improving the scratch resistance of polycarbonate is usually talcum powder. The principle that the talcum powder improves the scratch resistance of polycarbonate is to endow the surface of the polycarbonate material with smoothness, so that the friction coefficient of the surface of the material is reduced, and the surface friction is reduced, so that the scratch resistance is improved. However, the scratch resistance of the talc powder to the polycarbonate material is limited, and the higher scratch resistance requirement of the polycarbonate material cannot be met, so that the application of the polycarbonate material is limited, for example, the application of the polycarbonate material in the fields of mobile phone shells and high-grade electrical appliance panels.
Disclosure of Invention
In order to further effectively improve the scratch resistance of the polycarbonate material and further widen the application field of the polycarbonate material, the application provides a modified polycarbonate resin, a product thereof and a preparation method thereof.
In a first aspect, the present application provides a modified polycarbonate resin, which adopts the following technical scheme:
a modified polycarbonate resin comprises the following raw materials in parts by weight:
polycarbonate resin: 100 portions of
Acrylonitrile-styrene-acrylate copolymer: 0.8 to 1.5 portions of
acrylonitrile-styrene-N-phenylmaleimide copolymer: 0.5 to 1.2 portions of
Antioxidant: 0.5 to 1 portion
Anti-ultraviolet agent: 0.5 to 1 portion
The melt index of the polycarbonate resin is 6-12g/10min;
the melt index of the acrylonitrile-styrene-acrylate copolymer is 8-12g/10min;
the acrylonitrile-styrene-N-phenylmaleimide copolymer has a melt index of 6-10g/10min.
According to the application, the acrylonitrile-styrene-acrylate copolymer and the acrylonitrile-styrene-N-phenyl maleimide copolymer are used for modifying the polycarbonate resin material in a synergistic manner, so that the hardness of the modified polycarbonate resin is effectively improved to 3H, the low-temperature impact resistance of the modified polycarbonate is effectively improved, and the application of the polycarbonate material in the field of mobile phone shells or high-grade electrical appliance panels is widened. When the raw materials in the melt index range are selected, the raw materials have good compatibility, and the performance of the modified polycarbonate is improved.
Optionally, the polycarbonate comprises a polycarbonate resin with a melt index of 6-8g/10min and a polycarbonate resin with a melt index of 8-12g/10min, and the weight ratio of the polycarbonate resin with a melt index of 6-8g/10min to the polycarbonate resin with a melt index of 8-12g/10min is 3: (1-2).
When the polycarbonate resin is the polycarbonate resin in the above-mentioned proportion range, the hardness, the high temperature resistance and the impact resistance of the polycarbonate material are further improved, probably because the compatibility between the raw materials is further improved.
Optionally, the modified polycarbonate resin further comprises 1-2 parts by weight of silica whiskers.
The addition of the silicon dioxide whiskers into the modified polycarbonate resin is not only beneficial to improving the hardness of the polycarbonate material, but also beneficial to improving the high temperature resistance and the shock resistance of the polycarbonate resin.
Optionally, the silica whisker is a modified silica whisker, and the preparation method of the modified silica whisker comprises the following steps:
adding 30-50 parts by weight of methyl methacrylate and 3-5 parts by weight of polyvinylpyrrolidone K30 into 100 parts by weight of ethanol solution to obtain mixed solution A, introducing nitrogen to remove air in the mixed solution A, heating the mixed solution A until the temperature reaches 65 ℃, and preserving heat;
respectively adding 0.3-0.5 part by weight of trithiocarbonate RAFT reagent, 15-30 parts by weight of tripropylene glycol diacrylate and 10-20 parts by weight of acrylic acid into 100 parts by weight of ethanol solution to obtain mixed solution B, introducing nitrogen to remove air in the mixed solution B, heating the mixed solution B until the temperature reaches 65 ℃, and then preserving heat for 30-60min;
adding the mixed solution B after heat preservation into the mixed solution A during heat preservation, uniformly stirring, adding 0.5-0.8 part by weight of azobisisobutyronitrile, keeping the temperature of the system at 60-65 ℃, stirring for reacting for 20-30min, adding 3-5 parts by weight of silicon dioxide whiskers, and continuously stirring for reacting for 2-4h; and after the reaction is finished, carrying out centrifugal treatment, cleaning the centrifuged precipitate with ethanol and deionized water, and drying the cleaned product in vacuum at 50 ℃ to obtain the modified silicon dioxide crystal whisker.
Compared with the silicon dioxide whiskers, the modified silicon dioxide whisker polycarbonate resin has better compatibility, and meanwhile, the modified silicon dioxide whiskers and the polycarbonate resin have stronger bonding stability, so that the high temperature resistance, the impact resistance and the low-temperature impact resistance of the modified polycarbonate resin are effectively improved.
Optionally, the heating rate of the mixed solution A and the mixed solution B is controlled to be 0.5-1.0 ℃/min.
The high temperature resistance, the impact resistance and the low-temperature impact resistance of the modified polycarbonate resin can be further improved by controlling the heating rates of the mixed solution A and the mixed solution B.
Optionally, the antioxidant comprises any one or a combination of two of antioxidant 1010 and antioxidant 168.
The antioxidant 1010 is a high molecular weight hindered phenol antioxidant, has very low volatility, can improve the discoloration resistance of the polymer material under high temperature processing conditions, and effectively prevents thermal oxidative degradation of the polymer material during long-term aging. The antioxidant 168 can be provided to effectively decompose hydroperoxides generated during thermal processing of the polymeric material. Both antioxidant 1010 and antioxidant 168 can be effective in improving the processing stability of the polymeric material.
Optionally, the anti-ultraviolet agent is selected from one or a combination of two of an ultraviolet absorber UV531 and an ultraviolet absorber UV360.
The ultraviolet absorbers UV531 and UV360 have good compatibility with polycarbonate resin, and are favorable for improving the stability of the modified polycarbonate.
In a second aspect, the present application provides a method for preparing a modified polycarbonate resin, which adopts the following technical scheme:
a method for preparing a modified polycarbonate resin, comprising the steps of:
drying the polycarbonate resin;
uniformly mixing the dried polycarbonate resin with an acrylonitrile-styrene-acrylate copolymer, an acrylonitrile-styrene-N-phenylmaleimide copolymer, an antioxidant and an anti-ultraviolet agent to obtain a premix;
and granulating and drying the premix after melt extrusion to obtain the modified polycarbonate resin.
In a third aspect, the two-layer co-extrusion high-hardness polycarbonate sheet provided by the application adopts the following technical scheme: a two-layer co-extrusion high-hardness polycarbonate sheet comprises a modified polycarbonate layer and a polycarbonate layer, wherein the modified polycarbonate layer is made of any one of the modified polycarbonate resins, and the polycarbonate layer is made of a common polycarbonate resin.
In a fourth aspect, the preparation method of the two-layer co-extrusion high-hardness polycarbonate sheet provided by the application adopts the following technical scheme:
a preparation method of a two-layer co-extrusion high-hardness polycarbonate sheet comprises the following steps:
adding the modified polycarbonate resin into an extruder A for melting, wherein the temperature of the extruder A is set to be 270-290 ℃, and the rotating speed of the extruder A is 10-15r/min;
putting the common polycarbonate resin into an extruder B for melting, wherein the temperature of the extruder B is set to be 260-280 ℃, and the rotating speed of the extruder B is 45-50r/min;
connecting a die head distributor with an extruder A and an extruder B, enabling the melt of the modified polycarbonate resin to pass through the upper layer of the die head distributor, enabling the melt of the common polycarbonate resin to pass through the lower layer of the die head distributor, compounding the two layers, and then co-extruding from a die lip to obtain the high-hardness polycarbonate sheet.
To sum up, the technical scheme of this application includes following beneficial effect:
1. according to the preparation method, the acrylonitrile-styrene-acrylate copolymer and the acrylonitrile-styrene-N-phenylmaleimide copolymer are used for synergistically modifying the polycarbonate resin material, so that the hardness of the modified polycarbonate resin is effectively improved, and the scratch resistance of the modified polycarbonate is improved. In addition, compared with the method for modifying the polycarbonate by using a single acrylonitrile-styrene-acrylate copolymer or a single acrylonitrile-styrene-N-phenylmaleimide copolymer, the method for modifying the polycarbonate resin material by using the acrylonitrile-styrene-acrylate copolymer and the acrylonitrile-styrene-N-phenylmaleimide copolymer is more beneficial to improving the low-temperature impact resistance of the modified polycarbonate resin.
2. The high-temperature resistance, the shock resistance and the low-temperature shock resistance of the modified polycarbonate resin are further improved by adding the modified silicon dioxide whiskers.
Detailed Description
The present application will be described in further detail with reference to specific examples and comparative examples.
Examples
Examples 1 to 3
The formulation of each component of a modified polycarbonate resin in examples 1 to 3 is shown in Table 1 below.
TABLE 1 compounding ratio (unit/kg) of components of modified polycarbonate resins in examples 1 to 3
| Components | Example 1 | Example 2 | Example 3 |
| Polycarbonate resin | 100 | 100 | 100 |
| Acrylonitrile-styrene-acrylate copolymers | 0.8 | 1.1 | 1.5 |
| Acrylonitrile-styrene-N-phenylmaleimide copolymer | 1.2 | 0.9 | 0.5 |
| Antioxidant agent | 0.5 | 0.75 | 1 |
| Anti-ultraviolet agent | 1 | 0.75 | 0.5 |
Wherein the polycarbonate resin has a melt index of 6g/10min;
the melt index of the acrylonitrile-styrene-acrylate copolymer is 9g/10min;
the melt index of the acrylonitrile-styrene-N-phenylmaleimide copolymer is 8g/10min;
the antioxidants comprise an antioxidant 1010 and an antioxidant 168, and the weight ratio of the antioxidant 1010 to the antioxidant 168 is 3;
the uvioresistant agent is ultraviolet absorbent UV360.
The preparation method of the modified polycarbonate resin comprises the following steps:
drying the polycarbonate resin at the temperature of 100-120 ℃ for 2-4h, wherein the drying temperature is 110 ℃ for 2h in the embodiment;
uniformly mixing the dried polycarbonate resin with an acrylonitrile-styrene-acrylate copolymer, an acrylonitrile-styrene-N-phenylmaleimide copolymer, an antioxidant and an anti-ultraviolet agent according to the proportion in the table 1 to obtain a premix;
and (3) melting and extruding the premix at 230-250 ℃, granulating and drying to obtain the modified polycarbonate resin.
Example 4
A modified polycarbonate resin, which is different from example 2 in that:
the melt index of the polycarbonate resin was 8.4g/10min.
Example 5
A modified polycarbonate resin, which is different from example 2 in that:
the melt index of the polycarbonate resin was 12g/10min.
Example 6
A modified polycarbonate resin, which is different from example 4 in that:
the polycarbonate resin comprises polycarbonate resin with a melt index of 6g/10min and polycarbonate resin with a melt index of 12g/10min, and the weight ratio of the polycarbonate resin with the melt index of 6g/10min to the polycarbonate resin with the melt index of 12g/10min is 3.
Example 7
A modified polycarbonate resin differing from example 4 in that:
the polycarbonate resin comprises a polycarbonate resin with a melt index of 7g/10min and a polycarbonate resin with a melt index of 10g/10min, and the weight ratio of the polycarbonate resin with the melt index of 7g/10min to the polycarbonate resin with the melt index of 10g/10min is 8.
Example 8
A modified polycarbonate resin, which is different from example 6 in that:
1.5kg of silicon dioxide whiskers are also added, and the average length of the silicon dioxide whiskers is 50-60um.
Example 9
A modified polycarbonate resin which is different from example 8 in that:
the silicon dioxide crystal whisker is replaced by modified silicon dioxide crystal whisker with the same quantity, average length and the like, and the preparation method of the modified silicon dioxide crystal whisker comprises the following steps:
(1) Adding 30g of methyl methacrylate and 3g of polyvinylpyrrolidone K30 into 100g of ethanol solution with the volume fraction of 50% to obtain mixed solution A, introducing nitrogen to remove air in the mixed solution A, heating the mixed solution A, controlling the heating rate at 2 ℃/min during heating until the temperature reaches 65 ℃, and then preserving heat;
(2) Respectively adding 0.3g of S-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -azophenyl acetate) -trithiocarbonate, 15g of tripropylene glycol diacrylate and 10g of acrylic acid into 100g of ethanol solution with the volume fraction of 50% to obtain mixed solution B, introducing nitrogen to remove air in the mixed solution B, heating the mixed solution B, controlling the heating rate at 2 ℃/min during heating until the temperature reaches 65 ℃, and then preserving heat for 40min;
(3) Adding the mixed solution B after heat preservation into the mixed solution A during heat preservation, uniformly stirring, adding 0.5g of azodiisobutyronitrile, keeping the temperature of the system at 60-65 ℃, stirring for reacting for 25min, adding 3g of silicon dioxide whiskers, and continuously stirring for reacting for 2h; and after the reaction is finished, carrying out centrifugal treatment, cleaning the centrifuged precipitate with ethanol and deionized water, and drying the cleaned product in vacuum at 50 ℃ to obtain the modified silicon dioxide crystal whisker.
Example 10
A modified polycarbonate resin which is different from example 8 in that:
the silicon dioxide crystal whisker is replaced by modified silicon dioxide crystal whisker with the same quantity and average length, and the preparation method of the modified silicon dioxide crystal whisker comprises the following steps:
(1) Adding 50g of methyl methacrylate and 5g of polyvinylpyrrolidone K30 into 100g of ethanol solution with the volume fraction of 50% to obtain mixed solution A, introducing nitrogen to remove air in the mixed solution A, heating the mixed solution A, controlling the heating rate at 2 ℃/min during heating until the temperature reaches 65 ℃, and then preserving heat;
(2) Respectively adding 0.5g of S-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -azophenyl acetate) -trithiocarbonate, 30g of tripropylene glycol diacrylate and 20g of acrylic acid into 100g of ethanol solution with the volume fraction of 50% to obtain a mixed solution B, introducing nitrogen to remove air in the mixed solution B, heating the mixed solution B, controlling the heating rate at 2 ℃/min during heating until the temperature reaches 65 ℃, and then preserving the heat for 40min;
(3) Adding the mixed solution B after heat preservation into the mixed solution A during heat preservation, uniformly stirring, adding 0.8g of azodiisobutyronitrile, keeping the temperature of the system at 60-65 ℃, stirring for reacting for 25min, adding 5g of silicon dioxide whiskers, and continuously stirring for reacting for 2h; and after the reaction is finished, carrying out centrifugal treatment, cleaning the centrifuged precipitate by using ethanol and deionized water, and drying the cleaned product in vacuum at 50 ℃ to obtain the modified silicon dioxide whisker.
Example 11
A modified polycarbonate resin which is different from example 10 in that:
the heating rate of the mixed solution A and the mixed solution B is controlled at 0.75 ℃/min.
Example 12
A modified polycarbonate resin which is different from example 10 in that:
in the step 3, after the azobisisobutyronitrile is added, the system temperature is maintained at 80 ℃.
Example 13
A modified polycarbonate resin which is different from example 10 in that:
the modified silicon dioxide whisker is replaced by a copolymer of equivalent amount of methyl methacrylate, tripropylene glycol diacrylate and acrylic acid, and the preparation method of the copolymer of methyl methacrylate, tripropylene glycol diacrylate and acrylic acid comprises the following steps:
(1) Adding 50g of methyl methacrylate and 5g of polyvinylpyrrolidone K30 into 100g of ethanol solution with the volume fraction of 50% to obtain mixed solution A, introducing nitrogen to remove air in the mixed solution A, heating the mixed solution A, controlling the heating rate at 2 ℃/min during heating until the temperature reaches 65 ℃, and then preserving heat;
(2) Respectively adding 0.5g of S-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -azophenyl acetate) -trithiocarbonate, 30g of tripropylene glycol diacrylate and 20g of acrylic acid into 100g of ethanol solution with the volume fraction of 50% to obtain a mixed solution B, introducing nitrogen to remove air in the mixed solution B, heating the mixed solution B, controlling the heating rate at 2 ℃/min during heating until the temperature reaches 65 ℃, and then preserving the heat for 40min;
(3) Adding the mixed solution B after heat preservation into the mixed solution A during heat preservation, uniformly stirring, adding 0.8g of azodiisobutyronitrile, keeping the temperature of the system at 60-65 ℃, and stirring for reaction for 2 hours; and after the reaction is finished, carrying out centrifugal treatment, cleaning the centrifuged precipitate with ethanol and deionized water, and drying the cleaned product in vacuum at 50 ℃ to obtain the copolymer of methyl methacrylate, tripropylene glycol diacrylate and acrylic acid.
Comparative example
Comparative example 1
A modified polycarbonate resin, which is different from example 1 in that:
the melt index of the acrylonitrile-styrene-acrylate copolymer is 6g/10min;
the acrylonitrile-styrene-N-phenylmaleimide copolymer had a melt index of 12g/10min.
Comparative example 2
A modified polycarbonate resin, which is different from example 1 in that:
the acrylonitrile-styrene-acrylate copolymer was replaced with an equal amount of acrylonitrile-styrene-N-phenylmaleimide copolymer.
Comparative example 3
A modified polycarbonate resin, which is different from example 1 in that:
the acrylonitrile-styrene-N-phenylmaleimide copolymer was replaced with an equivalent amount of acrylonitrile-styrene-acrylate copolymer.
Comparative example 4
A modified polycarbonate resin differing from example 1 in that:
the acrylonitrile-styrene-acrylate copolymer and the acrylonitrile-styrene-N-phenylmaleimide copolymer are respectively replaced by equal amount of talcum powder.
Application example
Application example 1
A two-layer co-extrusion high-hardness polycarbonate sheet comprises a modified polycarbonate layer and a polycarbonate layer, wherein the modified polycarbonate layer is prepared by melt extrusion of the modified polycarbonate resin in example 1, and the polycarbonate layer is prepared by melt extrusion of a common polycarbonate resin.
Specifically, the preparation method of the two-layer co-extrusion high-hardness polycarbonate sheet comprises the following steps:
adding the modified polycarbonate resin into an extruder A for melting, wherein the temperature of the extruder A is set to be 270-290 ℃, and the rotating speed of the extruder A is 10r/min;
putting the common polycarbonate resin into an extruder B for melting, wherein the temperature of the extruder B is set to be 260-280 ℃, and the rotating speed of the extruder B is 45r/min;
connecting a die head distributor with an extruder A and an extruder B, enabling the melt of the modified polycarbonate resin to pass through the upper layer of the die head distributor, enabling the melt of the common polycarbonate resin to pass through the lower layer of the die head distributor, and performing coextrusion on the two layers from a die lip after compounding to obtain a two-layer coextrusion high-hardness polycarbonate sheet.
Application example 2
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that:
the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 2.
Application example 3
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that:
the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 3.
Application example 4
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that:
the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 4.
Application example 5
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that:
the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 5.
Application example 6
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that:
the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 6.
Application example 7
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that:
the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 7.
Application example 8
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that:
the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 8.
Application example 9
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that: the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 9.
Application example 10
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that: the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 10.
Application example 11
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that: the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 11.
Application example 12
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that: the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 12.
Application example 13
A two-layer co-extruded high-hardness polycarbonate sheet is different from application example 1 in that: the modified polycarbonate layer was obtained by melt-extruding the modified polycarbonate resin in example 13.
Comparative application example
Comparative application example 1
A two-layer co-extruded polycarbonate sheet, differing from application example 1 in that:
the modified polycarbonate layer was prepared by melt-extruding the modified polycarbonate resin in comparative example 1.
Comparative application example 2
A two-layer co-extruded polycarbonate sheet, differing from application example 1 in that:
the modified polycarbonate layer was prepared by melt-extruding the modified polycarbonate resin in comparative example 2.
Comparative application example 3
A two-layer co-extruded polycarbonate sheet, differing from application example 1 in that:
the modified polycarbonate layer was prepared by melt-extruding the modified polycarbonate resin in comparative example 3.
Comparative application example 4
A two-layer co-extruded polycarbonate sheet, differing from application example 1 in that:
the modified polycarbonate layer was prepared by melt-extruding the modified polycarbonate resin in comparative example 4.
Performance test data
1. Scratch hardness: selecting the hardest pencil which can not be scratched or scratched by the modified polycarbonate by referring to ASTM D3363-00 Standard test method for hardness of coated Pencil, repeatedly scribing the scribed position by using the pencil until the modified polycarbonate is scratched, stopping scribing, and recording the total scribing times.
2. Vicat softening temperature: the Vicat softening temperature test was performed with reference to ISO 306/B50. Wherein, the higher the Vicat softening temperature, the better the dimensional stability of the material when heated and the smaller the thermal deformation.
3. Notched Izod impact strength (3.2 mm): the test was performed with reference to ASTM D256.
Combining example 1 with comparative example 1 and the data in table 2, it can be seen that the melt index of the acrylonitrile-styrene-acrylate copolymer and the acrylonitrile-styrene-N-phenylmaleimide copolymer affects the dispersion property with the polycarbonate resin, thereby affecting the hardness, temperature resistance, impact resistance and low temperature impact resistance of the modified polycarbonate resin.
Combining example 1 with comparative examples 2-4 and the data in table 2, it can be seen that the acrylonitrile-styrene-acrylate copolymer and the acrylonitrile-styrene-N-phenylmaleimide copolymer synergistically increase the hardness of the modified polycarbonate to 3H and effectively improve the low-temperature impact resistance of the modified polycarbonate, but the addition of a single acrylonitrile-styrene-acrylate copolymer or acrylonitrile-styrene-N-phenylmaleimide copolymer cannot achieve the effect.
Combining examples 2 and 4-7 with the data in Table 2, it can be seen that the polycarbonate comprises a polycarbonate resin having a melt index of 6-8g/10min and a polycarbonate resin having a melt index of 8-12g/10min, and the weight ratio of the polycarbonate resin having a melt index of 6-8g/10min to the polycarbonate resin having a melt index of 8-12g/10min is in the range of 3: when the content is within the range of (1-2), the hardness, the high temperature resistance and the impact resistance of the polycarbonate material are further improved.
Combining example 6 with example 8 and the data in table 2, it can be seen that the addition of silica whiskers to the modified polycarbonate resin slightly improved the hardness, high temperature resistance, and impact resistance of the polycarbonate material.
It can be seen from the data in table 2 in conjunction with examples 8-10 that the modified polycarbonate resin containing silica whiskers has better compatibility, and the modified polycarbonate resin containing silica whiskers has higher bonding stability with the polycarbonate resin, thereby effectively improving the high temperature resistance, impact resistance and low temperature impact resistance of the modified polycarbonate resin.
It is understood from the data in Table 2 in combination with examples 10 to 11 that the high temperature resistance, impact resistance and low temperature impact resistance of the modified polycarbonate resin can be further improved by controlling the temperature rise rate of the mixed solution A and the mixed solution B to be in the range of 0.5 to 1.0 ℃/min.
When the reaction temperature of the mixed solution a and the mixed solution B is out of the range of the present application, the effect of adding the modified silica whiskers is equivalent to the effect of adding the silica whiskers, as is clear from the combination of the data in table 2 with the combination of example 10 and example 12.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The modified polycarbonate resin is characterized by comprising the following raw materials in parts by weight:
polycarbonate resin: 100 portions of
Acrylonitrile-styrene-acrylate copolymer: 0.8 to 1.5 portions of
acrylonitrile-styrene-N-phenylmaleimide copolymer: 0.5 to 1.2 portions of
Antioxidant: 0.5 to 1 portion
Anti-ultraviolet agent: 0.5 to 1 portion
The melt index of the polycarbonate resin is 6-12g/10min;
the melt index of the acrylonitrile-styrene-acrylate copolymer is 8-12g/10min;
the acrylonitrile-styrene-N-phenylmaleimide copolymer has the melt index of 6-10g/10min.
2. The modified polycarbonate resin according to claim 1, wherein: the polycarbonate comprises polycarbonate resin with a melt index of 6-8g/10min and polycarbonate resin with a melt index of 8-12g/10min, and the weight ratio of the polycarbonate resin with the melt index of 6-8g/10min to the polycarbonate resin with the melt index of 8-12g/10min is 3: (1-2).
3. The modified polycarbonate resin according to any one of claims 1 to 2, wherein: the modified polycarbonate resin also comprises 1-2 parts by weight of silicon dioxide whiskers.
4. The modified polycarbonate resin according to claim 3, wherein: the silicon dioxide whisker is modified silicon dioxide whisker, and the preparation method of the modified silicon dioxide whisker comprises the following steps:
adding 30-50 parts by weight of methyl methacrylate and 3-5 parts by weight of polyvinylpyrrolidone K30 into 100 parts by weight of ethanol solution to obtain mixed solution A, introducing nitrogen to remove air in the mixed solution A, heating the mixed solution A until the temperature reaches 65 ℃, and then preserving heat;
respectively adding 0.3-0.5 part by weight of trithiocarbonate RAFT reagent, 15-30 parts by weight of tripropylene glycol diacrylate and 10-20 parts by weight of acrylic acid into 100 parts by weight of ethanol solution to obtain a mixed solution B, introducing nitrogen to remove air in the mixed solution B, heating the mixed solution B until the temperature reaches 65 ℃, and then preserving heat for 30-60min;
adding the mixed solution B after heat preservation into the mixed solution A during heat preservation, uniformly stirring, adding 0.5-0.8 part by weight of azodiisobutyronitrile, keeping the temperature of the system at 60-65 ℃, stirring for reaction for 20-30min, adding 3-5 parts by weight of silicon dioxide whiskers, and continuing stirring for reaction for 2-4h; and after the reaction is finished, carrying out centrifugal treatment, cleaning the centrifuged precipitate with ethanol and deionized water, and drying the cleaned product in vacuum at 50 ℃ to obtain the modified silicon dioxide crystal whisker.
5. The modified polycarbonate resin according to claim 4, wherein: the heating and temperature rising speed of the mixed solution A and the mixed solution B is controlled to be 0.5-1.0 ℃/min.
6. The modified polycarbonate resin according to claim 1, wherein: the antioxidant comprises any one or a combination of two of an antioxidant 1010 and an antioxidant 168.
7. The modified polycarbonate resin according to claim 1, wherein: the uvioresistant agent is one or a combination of two of ultraviolet absorbent UV531 and ultraviolet absorbent UV360.
8. The method for preparing a modified polycarbonate resin according to any one of claims 1 to 7, wherein: the method comprises the following steps:
drying the polycarbonate resin;
uniformly mixing the dried polycarbonate resin with an acrylonitrile-styrene-acrylate copolymer, an acrylonitrile-styrene-N-phenylmaleimide copolymer, an antioxidant and an anti-ultraviolet agent to obtain a premix;
and granulating and drying the premix after melt extrusion to obtain the modified polycarbonate resin.
9. A two-layer co-extrusion high-hardness polycarbonate sheet is characterized in that: comprising a modified polycarbonate layer made of a modified polycarbonate resin as claimed in any one of claims 1 to 7 and a polycarbonate layer made of a general polycarbonate resin.
10. The preparation method of the two-layer co-extrusion high-hardness polycarbonate sheet material as claimed in claim 9, wherein the method comprises the following steps: the method comprises the following steps:
adding the modified polycarbonate resin into an extruder A for melting, wherein the temperature of the extruder A is set to be 270-290 ℃, and the rotating speed of the extruder A is 10-15r/min;
putting the common polycarbonate resin into an extruder B for melting, wherein the temperature of the extruder B is set to be 260-280 ℃, and the rotating speed of the extruder B is 45-50r/min;
connecting a die head distributor with extruders A and B, enabling the melt of the modified polycarbonate resin to pass through the upper layer of the die head distributor, enabling the melt of the common polycarbonate resin to pass through the lower layer of the die head distributor, and performing coextrusion on the two layers from a die lip after compounding to obtain the high-hardness polycarbonate sheet.
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