CN101935424B - ABS (Acrylonitrile Butadiene Styrene) thermoplastic resin and preparation method thereof - Google Patents
ABS (Acrylonitrile Butadiene Styrene) thermoplastic resin and preparation method thereof Download PDFInfo
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title claims abstract description 28
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title abstract description 25
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 28
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 230000002087 whitening effect Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 10
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- -1 whiteruss Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000004200 microcrystalline wax Substances 0.000 claims description 2
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- 229940113162 oleylamide Drugs 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 abstract description 21
- 229920006351 engineering plastic Polymers 0.000 abstract description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004611 light stabiliser Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 19
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 16
- 235000006708 antioxidants Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 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 description 1
- 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 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of polymer engineering plastics and particularly relates to an ABS (Acrylonitrile Butadiene Styrene) thermoplastic resin and a preparation method thereof. The invention solves the technical problem to provide an ABS thermoplastic resin with high fluidity and high transparency. The ABS thermoplastic resin is prepared from the raw materials in parts by weight: 20-75 parts of SAN (Styrene Acrylonitrile) resin, 20-60 parts of PMMA (Polymethylmethacrylate) resin, 2-25 parts of MBS (Methacrylate-butadiene-stryrene) resin, 0.2-04 part of antioxidant, 0.05-0.2 part of light stabilizer, 0.05-0.2 part of whitening agent and 0.05-0.2 part of lubricant. The ABS thermoplastic resin has the advantages of good surface glossiness, good rigidity, good transparency, good mechanical property and good forming and processing property, and each key index of the ABS thermoplastic resin exceeds that of commonly used transparent plastics such as transparent ABS and the like.
Description
Technical field
The invention belongs to macromolecule engineering plastics technology field, particularly ABS thermoplastic resin and preparation method thereof.
Background technology
ABS resin (acrylonitrile-butadiene-styrene (ABS)) is a kind of novel universal thermoplastic engineering plastic of the exploitation forties in 20th century, it has good electrical property, chemical resistant properties, shock-resistance, low temperature tolerance characteristics, winter hardiness, surface gloss, tinctorial property and dimensional stability, be easy to machine-shaping, the rich excellent glossiness of goods, and have toughness and flexibility concurrently.Therefore, ABS resin is widely used in shell and driving member, office appliance, instrument and other field of household electrical appliances, industrial spare and accessory parts, electric equipment products.
Along with constantly bringing forth new ideas and the continuous progress of state of the art of product design, research and application to transparent material increase gradually, and common ABS resin is normally opaque, therefore the application of ABS resin in transparency is had relatively high expectations the field is greatly limited, therefore usually adopt other transparent resins, as: PP (polypropylene), PMMA (polymethylmethacrylate), PS (polystyrene), PC (polycarbonate), SAN (vinylbenzene--vinyl cyanide), K-resin etc.
For above several transparent materials, although PP, PMMA, PS, SAN and K-resin occupy certain advantage aspect cost, and the transparency of material also can reach requirement, but their impact property is poor, and the PP shrinking percentage is larger, and this has limited them to a certain extent in much application in fields.And for PC, although it has excellent impact property and the transparency of material also can reach requirement, the too high and Drawing abillity of its cost and chemical resistant properties are all relatively poor, have therefore also limited its Application Areas.The development of Transparent ABS Resin therefore researcher has begun to be correlated with, about the method for modifying of Transparent ABS Resin, specifically can be divided into polyreaction method (as: Chinese patent 02802719.1) and modification processing method (as: Chinese patent: 200680055750.2, No. the 4767833rd, United States Patent (USP), Korean Patent No. 0429062, No. 0519116, No. the 703525th, European patent etc.) at present.The ABS with special construction that must use common ABS in above these patents or prepare by polyreaction is as base material, experimentation is cumbersome, complex operation, and the mobility of the Transparent ABS Resin that obtains and transparency can not reach good coordination and unification.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of ABS thermoplastic resin with high workability and high transparent, and this ABS thermoplastic resin is that the following raw materials in parts by weight ratio makes:
20～75 parts of SAN resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
0.2～0.4 part of antioxidant;
0.05～0.2 part of photostabilizer;
0.05～0.2 part, whitening agent;
0.05～0.2 part of lubricant.
Preferably, this ABS thermoplastic resin is that the following raw materials in parts by weight ratio makes:
35～75 parts of SAN resins;
20～50 parts of PMMA resins;
4～18 parts of MBS resins;
0.2～0.3 part of antioxidant;
0.05～0.1 part of photostabilizer;
0.05～0.1 part, whitening agent;
0.05～0.1 part of lubricant.
Wherein, the refractive index of described PMMA resin is that the refractive index of 1.4～1.6, SAN resin is 1.5～1.7.
Described PMMA resin is polymethylmethacrylate, the heat-resisting level of injection moulding, and its Vicat softening point is greater than 110 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min.
Described SAN resin is styrene-acrylonitrile copolymer, and wherein the content of vinyl cyanide is 15～24%, and Vicat softening point is greater than 105 ℃.
Described MBS resin is toughner, be specially methyl acrylate-butadiene-styrene copolymer, for having the transparent material of nucleocapsid structure, wherein the weight percent content of methyl acrylate is 5～45%, butadiene content is 10～40%, and styrene content is 15～60%.
The refractive index deviation control that adds tunable PMMA and SAN resin of MBS resin is in 0.005, the refractive index that is about to three material is compromised to a certain concrete numerical value, due to PMMA and the SAN consistency fabulous, can suitably adjust the ratio of PMMA and SAN, can add according to the demand of material property the MBS of different marks simultaneously, because the MBS refractive index that adds is between PMMA and SAN, therefore the coordinative role by MBS can be with the refractive index deviation control of PMMA in body series and SAN resin in 0.005.
Described antioxidant can adopt hindered phenol antioxidant, the preferred model that adopts is that 1010 hindered phenol antioxidant is as main anti-oxidant, model be 168 hindered phenol antioxidant as auxiliary antioxidant, main anti-1010 and auxiliary anti-168 by the weight ratios preparation of 3: 1.
Described photostabilizer can adopt sebacic acid two 2,2,6,6-tetramethyl piperidine alcohol ester, two (1,2,2,6,6-pentamethyl--4-piperidines) sebate, 1-methyl-8-(1,2,2,6,6-pentamethyl--4-piperidines) sebate, 2,2, at least a in 6,6-tetramethyl piperidine nitrogen oxygen free radical; Two 2,2,6, the 6-tetramethyl piperidine alcohol esters of preferred sebacic acid.
Described whitening agent can adopt fluorescent whitening agent OB-1, fluorescent whitening agent OB C, white dyes KSN, white dyes KCB, fluorescent whitening agent OB S etc., preferred white dyes 0B-1.
Described lubricant can adopt stearic acid, butyl stearate, oleylamide, ethylene bis stearamide, native paraffin, whiteruss (white oil), microcrystalline wax, polyethylene wax, low-molecular-weight polypropylene etc., preferred ethylene bis stearamide.
The present invention has reasonably regulated the formula of alloy material, and SAN and the PMMA resin of selecting refractive index to approach, and the per-cent of control SAN, PMMA and MBS composition provide a kind of thermoplastic resin with high workability and high transparent.
Second technical problem solved by the invention is to provide the preparation method of above-mentioned ABS thermoplastic resin, and after the method is specially following raw material mixing, fusing and pelleting gets;
20～75 parts of SAN resins;
20～60 parts of PMMA resins;
2～25 parts of MBS resins;
0.2～0.4 part of antioxidant;
0.05～0.2 part of photostabilizer;
0.05～0.2 part, whitening agent;
0.05～0.2 part of lubricant.
Need dry in raw material before SAN resin, PMMA resin and MBS mixed with resin.Preferably, drying temperature is 70～90 ℃; Optimum drying temperature is 80 ℃, 3～6 hours time of drying.
High-speed mixing is adopted in described mixing, and mixing time is 1～6 minute, preferred 2 minutes.
The Heating temperature of described melt pelletization is 160～245 ℃, and head temperature is 215 ℃.Main-machine screw rotating speed 450～550r/min, reinforced rotating speed 45～55r/min.
The present invention adopts the method for blending and modifying, utilize direct labor engineering plastics SAN, PMMA, MBS etc. to make disperse phase (rubber composition by the method that melt extrudes, divinyl in MBS) and external phase (matrix resin, SAN and PMMA resin) between refractive index be complementary (the refractive index deviation control in whole system is in 0.005), thereby make between disperse phase and external phase the refraction of light at the interface and diffusion be reduced to minimum.The thermoplastic resin for preparing possesses good surface gloss, hardness and transparency, mechanical property and moulding processability, and every key index is all over transparent plasticss commonly used such as transparent ABSs.
Embodiment
The starting material consumption of each embodiment sees Table 1:
Table 1 unit: kilogram
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PMMA | 23.75 | 35 | 45 | 49.5 |
| SAN | 71.25 | 55 | 40 | 49.5 |
| MBS | 5 | 10 | 15 | 1 |
| Antioxidant 1010/168 | 0.2 | 0.2 | 0.2 | 0.2 |
| Two 2,2,6, the 6-tetramethyl piperidine alcohol esters of sebacic acid | 0.08 | 0.08 | 0.08 | 0.08 |
| Fluorescent whitening agent OB-1 | 0.07 | 0.07 | 0.07 | 0.07 |
| Ethylene bis stearamide | 0.05 | 0.05 | 0.05 | 0.05 |
The compound proportion of antioxidant is 1010 by weight: 168=3: 1.
The total content of photostabilizer, whitening agent, lubricant is: 0.2%
Embodiment 1
take various raw materials according to table 1 composition of raw materials, wherein (weight percent content of methyl acrylate is 5～45% to the MBS resin, butadiene content is 10～40%, styrene content is 15～60%), (refractive index is 1.492 to the PMMA resin, Vicat softening point is greater than 110 ℃, under the condition of 200 ℃/5Kg, its melting index is 1.5～3.5g/min), (refractive index is 1.56 to the SAN resin, the content of vinyl cyanide should be lower than 15～24%, Vicat softening point is greater than 105 ℃) be respectively before use 80 ℃ of dryings 3 hours, add the high-speed mixer high speed to mix 2 minutes various raw materials (comprising auxiliary material), low speed discharging again.Material after mixing gets the ABS thermoplastic resin composition of high workability, high transparent through fusing and pelleting, product property detects data and sees Table 2.The melt pelletization condition is: main-machine screw rotating speed 500r/min, reinforced rotating speed 50r/min, 1:160 ℃ of Heating temperature section design temperature, 2:190 ℃, 3:200 ℃, 4:225 ℃, 5:235 ℃, 6:245 ℃, 7:235 ℃, 8:225 ℃, 9:215 ℃, head temperature: 215 ℃.
The preparation method of embodiment 2～4 is identical with embodiment 1, and the product of 4 embodiment is tested according to GB, and correlation data is as shown in table 2:
Tensile strength is tested according to GB GB/T1040.2-2006; Flexural strength, modulus in flexure are tested according to GB GB/T9341-2000; The socle girder notched Izod impact strength is tested according to GB GB/T1843-2008; Heat-drawn wire is tested according to GB GB/T1634.2-2004; Melt flow rate (MFR) is tested according to GB GB/T3682-2000; Transparency is tested according to GB GB/T2410-2008.
Table 2
As can be seen from Table 2, ratio and composition by each component in reasonable control formula, add the transparency that effectively to control the gained thermoplastic resin composition in the situation of a certain amount of MBS, its toughness (shock strength) also can significantly improve, thereby realized the ABS thermoplastic resin composition's of high workability and high transparent preparation by the method for blending and modifying with lower cost, the method is simple to operate, required starting material are easy to get, and are the ABS thermoplastic resin composition's of preparation high workability and high transparent rare experimental technique.
But, embodiment 4 is because the add-on of MBS has exceeded scope of the present invention, and add-on is too little, although good mechanical property, melt flow rate (MFR) and the transparency are arranged, but the notched Izod impact strength of products obtained therefrom (being toughness) is too poor, can not be applied to actual production.
Claims (7)
1.ABS thermoplastic resin is characterized in that: thermoplastic resin is that the following raw materials in parts by weight ratio makes:
35～75 parts of SAN resins;
20～50 parts of PMMA resins;
4～18 parts of MBS resins;
0.2～0.3 part of antioxidant;
0.05～0.1 part of photostabilizer;
0.05～0.1 part, whitening agent;
0.05～0.1 part of lubricant;
Wherein, in the MBS resin, the weight percent content of methyl acrylate is 5～45%, and butadiene content is 10～40%, and styrene content is 15～60%;
PMMA resin Vicat softening point is greater than 110 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.5～3.5g/min; In the SAN resin, the content of vinyl cyanide is 15～24%, and Vicat softening point is greater than 105 ℃.
2. ABS thermoplastic resin according to claim 1, it is characterized in that: the refractive index of PMMA resin is that the refractive index of 1.4～1.6, SAN resin is 1.5～1.7.
3. ABS thermoplastic resin according to claim 1 is characterized in that: described antioxidant is the main anti-1010 and auxiliary anti-168 weight ratio preparations by 3:1; Described photostabilizer adopts sebacic acid two 2,2,6,6-tetramethyl piperidine alcohol ester, two (1,2,2,6,6-pentamethyl--4-piperidines) sebate, 1-methyl-8-(1,2,2,6,6-pentamethyl--4-piperidines) sebate, 2,2, at least a in 6,6-tetramethyl piperidine nitrogen oxygen free radical; Described whitening agent adopts fluorescent whitening agent OB-1, fluorescent whitening agent OB C, white dyes KSN, white dyes KCB or fluorescent whitening agent OB S; Described lubricant adopts stearic acid, butyl stearate, oleylamide, ethylene bis stearamide, native paraffin, whiteruss, microcrystalline wax, polyethylene wax or low-molecular-weight polypropylene.
4. the preparation method of ABS thermoplastic resin claimed in claim 1 is characterized in that: the method is that after following raw material mixes, fusing and pelleting gets;
35～75 parts of SAN resins;
20～50 parts of PMMA resins;
4～18 parts of MBS resins;
0.2～0.3 part of antioxidant;
0.05～0.1 part of photostabilizer;
0.05～0.1 part, whitening agent;
0.05～0.1 part of lubricant.
5. ABS thermoplastic resin according to claim 4 is characterized in that: need dryly before SAN resin, PMMA resin and MBS mixed with resin, drying temperature is 70～90 ℃.
6. ABS thermoplastic resin according to claim 5 is characterized in that: high-speed mixing is adopted in described mixing, and mixing time is 1～6 minute.
7. ABS thermoplastic resin according to claim 5, it is characterized in that: the Heating temperature of described melt pelletization is 160～245 ℃, head temperature is 215 ℃; Main-machine screw rotating speed 450～550r/min, reinforced rotating speed 45～55r/min.
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| CN102492255A (en) * | 2011-12-05 | 2012-06-13 | 四川长虹电器股份有限公司 | ABS/PMMA (Acrylonitrile Butadiene Styrene/Polymethyl Methacrylate) composite material and preparation method thereof |
| CN105885340B (en) * | 2014-12-26 | 2019-03-29 | 神华集团有限责任公司 | Antioxidant composition and modified polyformaldehyde resin composition and modified polyformaldehyde resin and preparation method thereof |
| CN105885339B (en) * | 2014-12-26 | 2019-03-29 | 神华集团有限责任公司 | Antioxidant composition and modified polyformaldehyde resin composition and modified polyformaldehyde resin and preparation method thereof |
| CN105504569A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | Wear-resistant ASA/PMMA (acrylonitrile-styrene-acrylate/polymethylmethacrylate) blend material with high weather resistance and high gloss and preparation method thereof |
| CN106280176A (en) * | 2016-08-29 | 2017-01-04 | 金旸（厦门）新材料科技有限公司 | A kind of novel transparent flame-proof ABS resin and preparation method thereof |
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