CN117986800A - High-gloss transparent ABS resin and preparation method thereof - Google Patents
High-gloss transparent ABS resin and preparation method thereof Download PDFInfo
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- CN117986800A CN117986800A CN202410217865.7A CN202410217865A CN117986800A CN 117986800 A CN117986800 A CN 117986800A CN 202410217865 A CN202410217865 A CN 202410217865A CN 117986800 A CN117986800 A CN 117986800A
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 63
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 46
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 238000002834 transmittance Methods 0.000 claims abstract description 27
- 239000005064 Low cis polybutadiene Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 82
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 239000002904 solvent Substances 0.000 claims description 75
- 239000003999 initiator Substances 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 51
- 239000007822 coupling agent Substances 0.000 claims description 43
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 41
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 41
- 239000012986 chain transfer agent Substances 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 38
- 239000003112 inhibitor Substances 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- 238000003860 storage Methods 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical group C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 24
- 239000003292 glue Substances 0.000 claims description 24
- 239000005049 silicon tetrachloride Substances 0.000 claims description 24
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- -1 alkyl lithium Chemical compound 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 150000003254 radicals Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 46
- 238000001035 drying Methods 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 238000010926 purge Methods 0.000 description 23
- 239000003607 modifier Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229920001971 elastomer Polymers 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000151 deposition Methods 0.000 description 13
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 11
- 238000005086 pumping Methods 0.000 description 11
- 238000010008 shearing Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000002902 bimodal effect Effects 0.000 description 7
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-gloss transparent ABS resin and a preparation method thereof. The high-gloss transparent ABS resin comprises the following raw materials in parts by weight: styrene, star-shaped low cis polybutadiene rubber: acrylonitrile: methyl methacrylate: the weight ratio is 40-60:5-20:10-20:20-40. The preparation method comprises the steps of firstly adopting anion polymerization to synthesize star-shaped low cis-polybutadiene rubber, and then copolymerizing methyl methacrylate and styrene, acrylonitrile and star-shaped low cis-polybutadiene rubber into high-gloss transparent ABS resin. The molecular weight of the ABS resin synthesized by the method is 70-200kg/mol, the light transmittance is 85% -90%, and the glossiness (60 ℃) is 96-109GU. Has the advantages of high gloss, high transparency, high impact strength and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of functionalized polymer materials, and particularly relates to a high-gloss transparent ABS resin and a preparation method thereof.
Background
ABS is a three-component thermoplastic resin of a typical two-phase structure consisting of a SAN continuous phase and a dispersed rubber phase. The rubber phase particles are grafted with a portion of the monomer to form the necessary interfacial adhesion between the non-grafted copolymer matrix and to promote uniform dispersion of the colloidal particles in the matrix. The ABS resin adopts low cis-polybutadiene rubber as toughening rubber, and the impact resistance of the prepared ABS resin is difficult to ensure; the transparent ABS resin generally adopts linear rubber as toughening rubber, but the linear rubber can not achieve the problems of high gloss and high impact strength, and has the defects of low mechanical strength, poor glossiness and the like. Therefore, how to solve the problems of poor mechanical properties and poor glossiness caused by small-particle-size rubber in transparent ABS resin, and better give consideration to the glossiness and impact strength of the ABS resin, and provide a high-glossiness transparent ABS resin and a preparation method thereof, which are technical problems to be solved in the field.
Disclosure of Invention
In order to solve the problem of poor mechanical property and glossiness existing in the process of preparing transparent ABS resin in the prior art, and to consider the uniformity of the glossiness and impact strength properties of the ABS resin, the invention provides a high-glossiness transparent ABS resin and a preparation method thereof. The invention uses star-shaped low cis-polybutadiene rubber as a toughening agent, and prepares the transparent ABS resin material with high gloss by free radical polymerization of methyl methacrylate, styrene and acrylonitrile. Compared with other types of rubber toughening agents, the ABS resin obtained under the condition of the same particle size has the characteristics of impact resistance, high gloss, transparency and high impact resistance.
In a first aspect, the invention provides a high-gloss transparent ABS resin, which comprises the following components in parts by mass:
40-60 parts of styrene, 5-20 parts of star-shaped low cis-polybutadiene rubber, 10-20 parts of acrylonitrile and 20-40 parts of methyl methacrylate.
Further, the high-gloss transparent ABS resin comprises, by mass, 45-55 parts of styrene, 10-15 parts of star-shaped low cis-polybutadiene rubber, 13-15 parts of acrylonitrile and 25-35 parts of methyl methacrylate.
Further, the molecular weight of the star-shaped low cis-polybutadiene rubber is 100-600kg/mol.
Further, the high-gloss transparent ABS resin has a molecular weight of 70-200kg/mol, a light transmittance of 85% -90% and a glossiness (60 ℃) of 96-109GU.
Further, the star-shaped low cis-polybutadiene rubber is prepared by the following method: introducing cyclohexane and butadiene into a reaction kettle, wherein the reaction temperature is 50-60 ℃, the stirring speed is 150-200r/min, and adding an alkyl lithium initiator and tetrahydrofuran for reaction for 1-2 hours; then adding a coupling agent, reacting for 2-2.5 hours, and then adding isopropanol to terminate the reaction to obtain the star polybutadiene rubber;
The raw material components are proportioned according to the following parts by weight: 220-240 parts of cyclohexane, 25-30 parts of butadiene, 0.001-0.002 part of tetrahydrofuran, 0.1-0.2 part of alkyl lithium, 0.02-0.075 part of coupling agent and 0.09-0.10 part of isopropanol.
In a second aspect, the present invention provides a method for preparing a high gloss transparent ABS resin, comprising the steps of:
s1, S2, mixing and dissolving the prepared star-shaped low cis-polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and a solvent to obtain a mixed solution;
S3, adding the mixed solution, a free radical initiator and a chain transfer agent into a reactor;
and S4, after oxygen is discharged, stirring and heating are started, and after a certain time of reaction, the polymer is dissolved, deposited, crushed and dried, so that the high-gloss transparent ABS resin is obtained.
Further, the star-shaped low cis-polybutadiene rubber is prepared by the following method: introducing cyclohexane and butadiene into a reaction kettle, wherein the reaction temperature is 50-60 ℃, the stirring speed is 150-200r/min, and adding an alkyl lithium initiator and tetrahydrofuran for reaction for 1-2 hours; then adding a coupling agent, reacting for 2-2.5 hours, and then adding isopropanol to terminate the reaction, thus obtaining the star-shaped low cis-polybutadiene rubber.
Further, the star-shaped low cis-polybutadiene rubber comprises the following raw materials in parts by weight: 220-240 parts of cyclohexane, 25-30 parts of butadiene, 0.001-0.002 part of tetrahydrofuran, 0.1-0.2 part of alkyl lithium, 0.02-0.075 part of coupling agent and 0.09-0.10 part of isopropanol.
Further, the coupling agent is selected from silicon tetrachloride.
Further, the initiator is at least one of alkyl lithium initiators; n-butyllithium is preferred.
Further, the raw materials in the step S1 are proportioned according to the following parts by weight: 40-60 parts of styrene, 5-20 parts of star-shaped low cis-polybutadiene rubber, 10-20 parts of acrylonitrile and 20-40 parts of methyl methacrylate; the addition amount of the free radical initiator is 0.00002-0.00005 part; the chain transfer agent is added in an amount of 0.00005 to 0.00015 parts.
Further, the free radical initiator is di-tert-butyl peroxide;
the chain transfer agent is at least one of n-dodecyl mercaptan and tert-dodecyl mercaptan.
Further, the oxygen is discharged from the reactor by purging with nitrogen for 15-30 minutes.
Further, the solvent is at least one of ethylbenzene and xylene, and the solvent addition amount is 20-30 parts.
Further, the stirring speed in the step S3 is 180-600r/min, and the reaction temperature is 100-140 ℃; the reaction time is 4-8 hours.
Further, the solvent used for dissolving the polymer in the step S3 is at least one of N-methyl pyrrolidone and dichloromethane, preferably dichloromethane; the poor solvent used for depositing the gel is at least one of methanol and ethanol, preferably methanol; the glue depositing time is 4-12 hours, the drying time is 12-48 hours, and the drying temperature is 70-80 ℃.
Further, styrene, methyl methacrylate and acrylonitrile raw materials are firstly subjected to polymerization inhibitor removal by using alkaline alumina before use; the butadiene storage tank, the cyclohexane storage tank, the tetrahydrofuran and the isopropanol are strictly dehydrated and deoxidized.
Further, the polymerization inhibitor is removed by using an alkaline alumina chromatographic column.
The invention discloses a high-gloss transparent ABS resin prepared by the preparation method, wherein the molecular weight of the high-gloss transparent ABS resin is 70-200kg/mol, the light transmittance is 85% -90%, and the glossiness (60 ℃) is 96-109GU.
The invention has the beneficial effects that:
The application uses the synthesized star-shaped low cis-polybutadiene rubber as toughening rubber, and improves the light transmittance of the resin by changing the rubber component structure of the ABS resin. Under the condition of the same molecular weight, the star-shaped polybutadiene rubber has smaller particle size than the linear polybutadiene rubber, so that the light transmittance of the material can be improved; the star structure can form more grafting sites, which is more beneficial to improving the shock resistance of the ABS resin material. The star polybutadiene rubber synthesized by the application has better cold resistance, low-temperature flexibility, better grafting and crosslinking capability and stronger grafting capability with resin than common butadiene rubber due to the structural difference between the star polybutadiene rubber and the butadiene rubber; the light transmittance of the resin is improved on the basis of improving the impact strength of the resin; the low cis rubber of the four-arm structure enhances the combination of a resin phase and a rubber phase, thereby ensuring the excellent mechanical property of the transparent ABS resin. The ABS resin with transparency, high gloss and high impact strength is prepared, the defects of poor impact property and poor glossiness of the transparent ABS resin are overcome, and the ABS resin has wide application market and development potential.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.
Preferred embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention.
The experimental methods and calculation methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The performance testing instrument used in the embodiment of the invention comprises:
The molecular weight and the molecular weight distribution thereof are tested by adopting a Gel Permeation Chromatograph (GPC), TSK gel Super H-RC reference column, chromatographic pure THF is taken as a solvent, polystyrene is taken as a correction standard sample, the mass concentration of the sample is 2mg/mL, the sample injection amount is 20.00 mu L, the flow is 1mL/min, and the test temperature is 40.0 ℃;
Notched Izod impact strength (Izod) was tested according to GB/T1843-2008 standard; 60℃gloss is measured according to the GB 8807-1988 standard;
the transparent ABS resin was pressed into a sheet of 50 mm. Times.50 mm. Times.1 mm, and the transmittance of the ABS resin was measured by a transmittance haze meter, test standard GB/T2410-2008.
Example 1
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 220 parts of cyclohexane, 25 parts of butadiene, 0.001 part of tetrahydrofuran, 0.1 part of n-butyllithium, 0.02 part of silicon tetrachloride and 0.09 part of isopropanol. The reaction temperature was 60℃and the stirring rate was 200r/min. After adding the initiator and the regulator, the reaction is carried out for 2 hours, and then the coupling agent is added for 2.5 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 40 parts of styrene, 5 parts of star-shaped polybutadiene rubber, 10 parts of acrylonitrile and 20 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 20 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00002 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00005 part, and the nitrogen purging time is 15 minutes.
The stirring speed of the step (5) is 600r/min, and the reaction temperature is 140 ℃. The reaction time was 8 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 12 hours, the drying time is 48 hours, and the drying temperature is 80 ℃.
The polybutadiene rubber synthesized by the process and the formula has the bimodal molecular weight of 156kg/mol and 576kg/mol, the light transmittance of the high-gloss transparent ABS resin of 87%, the impact strength of 12.4kJ/m 2 and the glossiness of 102.6GU under a 60-degree test angle.
Example 2
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 220 parts of cyclohexane, 25 parts of butadiene, 0.001 part of tetrahydrofuran, 0.1 part of n-butyllithium, 0.02 part of silicon tetrachloride and 0.09 part of isopropanol. The reaction temperature was 50℃and the stirring rate was 150r/min. The initiator and modifier are added and reacted for 1 hour, and then the coupling agent is added and reacted for 2 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 40 parts of styrene, 5 parts of star-shaped polybutadiene rubber, 10 parts of acrylonitrile and 20 parts of methyl methacrylate, wherein the solvent is dimethylbenzene, the solvent addition amount is 20 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00002 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00005 part, and the nitrogen purging time is 15 minutes.
The stirring speed of the step (5) is 180r/min, and the reaction temperature is 100 ℃. The reaction time was 4 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 4 hours, the drying time is 12 hours, and the drying temperature is 70 ℃.
The polybutadiene rubber synthesized by the process and the formula has the bimodal molecular weight of 146kg/mol and 528kg/mol, the light transmittance of the high-gloss transparent ABS resin of 88%, the impact strength of 11.7kJ/m 2 and the glossiness of 103.6GU under a 60-degree test angle.
Example 3
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 240 parts of cyclohexane, 30 parts of butadiene, 0.002 part of tetrahydrofuran, 0.2 part of n-butyllithium, 0.075 part of silicon tetrachloride and 0.10 part of isopropanol. The reaction temperature was 60℃and the stirring rate was 200r/min. After adding the initiator and the regulator, the reaction is carried out for 2 hours, and then the coupling agent is added for 2.5 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 60 parts of styrene, 20 parts of star-shaped polybutadiene rubber, 20 parts of acrylonitrile and 40 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 30 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00005 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00015 part, and the nitrogen purging time is 30 minutes.
The stirring speed of the step (5) is 600r/min, and the reaction temperature is 140 ℃. The reaction time was 8 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 12 hours, the drying time is 48 hours, and the drying temperature is 80 ℃.
The polybutadiene rubber synthesized by the process and the formula has the molecular weight of 352kg/mol, the light transmittance of 89% and the impact strength of 11.3kJ/m 2, and the glossiness of 96.9GU under the test angle of 60 degrees.
Example 4
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 240 parts of cyclohexane, 30 parts of butadiene, 0.002 part of tetrahydrofuran, 0.2 part of n-butyllithium, 0.075 part of silicon tetrachloride and 0.10 part of isopropanol. The reaction temperature was 50℃and the stirring rate was 150r/min. The initiator and modifier are added and reacted for 1 hour, and then the coupling agent is added and reacted for 2 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 60 parts of styrene, 20 parts of star-shaped polybutadiene rubber, 20 parts of acrylonitrile and 40 parts of methyl methacrylate, wherein the solvent is xylene, the solvent addition amount is 30 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00005 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00015 part, and the nitrogen purging time is 15 minutes.
The stirring speed of the step (5) is 180r/min, and the reaction temperature is 100 ℃. The reaction time was 4 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 4 hours, the drying time is 12 hours, and the drying temperature is 70 ℃.
The polybutadiene rubber synthesized by the process and the formula has the molecular weight of 375kg/mol, the light transmittance of 88 percent, the impact strength of 11.8kJ/m 2 and the glossiness of 102.2GU under the test angle of 60 degrees.
Example 5
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 150 parts of cyclohexane, 30 parts of butadiene, 0.001 part of tetrahydrofuran, 0.1 part of n-butyllithium, 0.02 part of silicon tetrachloride and 0.09 part of isopropanol. The reaction temperature was 50℃and the stirring rate was 150r/min. The initiator and modifier are added and reacted for 1 hour, and then the coupling agent is added and reacted for 2 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 60 parts of styrene, 20 parts of star-shaped polybutadiene rubber, 20 parts of acrylonitrile and 40 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 30 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00005 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00015 part, and the nitrogen purging time is 30 minutes.
The stirring speed of the step (5) is 600r/min, and the reaction temperature is 140 ℃. The reaction time was 8 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 12 hours, the drying time is 48 hours, and the drying temperature is 80 ℃.
The polybutadiene rubber synthesized by the process and the formula has the bimodal molecular weight of 134kg/mol and 533kg/mol, the light transmittance of 88% and the impact strength of 11.0kJ/m 2, and the glossiness of 103.3GU under a 60-degree test angle.
Example 6
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 240 parts of cyclohexane, 30 parts of butadiene, 0.002 part of tetrahydrofuran, 0.2 part of n-butyllithium, 0.075 part of silicon tetrachloride and 0.10 part of isopropanol. The reaction temperature was 60℃and the stirring rate was 200r/min. After adding the initiator and the regulator, the reaction is carried out for 2 hours, and then the coupling agent is added for 2.5 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 40 parts of styrene, 5 parts of star-shaped polybutadiene rubber, 10 parts of acrylonitrile and 20 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 20 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00002 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00005 part, and the nitrogen purging time is 15 minutes.
The stirring speed of the step (5) is 180r/min, and the reaction temperature is 100 ℃. The reaction time was 4 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 4 hours, the drying time is 12 hours, and the drying temperature is 70 ℃.
The polybutadiene rubber synthesized by the process and the formula has the molecular weight of 364kg/mol, the light transmittance of 86 percent, the impact strength of 10.4kJ/m 2 and the glossiness of 108.8GU under the test angle of 60 degrees.
Example 7
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 220 parts of cyclohexane, 25 parts of butadiene, 0.001 part of tetrahydrofuran, 0.1 part of n-butyllithium, 0.02 part of silicon tetrachloride and 0.09 part of isopropanol. The reaction temperature was 60℃and the stirring rate was 200r/min. After adding the initiator and the regulator, the reaction is carried out for 2 hours, and then the coupling agent is added for 2.5 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 60 parts of styrene, 20 parts of star-shaped polybutadiene rubber, 20 parts of acrylonitrile and 40 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 30 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00005 part, the chain transfer agent is n-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00015 part, and the nitrogen purging time is 15 minutes.
The stirring speed of the step (5) is 180r/min, and the reaction temperature is 100 ℃. The reaction time was 4 hours. The poor solvent is ethanol, and the solvent used for dissolving the polymer is N-methyl pyrrolidone. The glue depositing time is 4 hours, the drying time is 12 hours, and the drying temperature is 70 ℃.
The polybutadiene rubber synthesized by the process and the formula has the bimodal molecular weight of 144kg/mol and 567kg/mol, the light transmittance of 87% and the impact strength of 11.6kJ/m 2, and the glossiness of 102.6GU under the test angle of 60 degrees.
Example 8
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 240 parts of cyclohexane, 30 parts of butadiene, 0.002 part of tetrahydrofuran, 0.2 part of n-butyllithium, 0.075 part of silicon tetrachloride and 0.10 part of isopropanol. The reaction temperature was 50℃and the stirring rate was 150r/min. The initiator and modifier are added and reacted for 1 hour, and then the coupling agent is added and reacted for 2 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 40 parts of styrene, 5 parts of star-shaped polybutadiene rubber, 10 parts of acrylonitrile and 20 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 20 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00002 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00005 part, and the nitrogen purging time is 30 minutes.
The stirring speed of the step (5) is 600r/min, and the reaction temperature is 140 ℃. The reaction time was 8 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 12 hours, the drying time is 48 hours, and the drying temperature is 80 ℃.
The polybutadiene rubber synthesized by the process and the formula has the molecular weight of 378kg/mol, the light transmittance of the high-gloss transparent ABS resin of 87%, the impact strength of 10.9kJ/m 2 and the glossiness of 97.9GU under a 60-degree test angle.
Example 9
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 230 parts of cyclohexane, 28 parts of butadiene, 0.0015 part of tetrahydrofuran, 0.15 part of n-butyllithium, 0.05 part of silicon tetrachloride and 0.095 part of isopropanol. The reaction temperature was 55deg.C and the stirring rate was 175r/min. The initiator and modifier were added and reacted for 1.5 hours, followed by the coupling agent for 2.25 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 50 parts of styrene, 12 parts of star-shaped polybutadiene rubber, 15 parts of acrylonitrile and 30 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 20 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00004 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00010 part, and the nitrogen purging time is 20 minutes.
The stirring speed of the step (5) is 400r/min, and the reaction temperature is 120 ℃. The reaction time was 6 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 8 hours, the drying time is 36 hours, and the drying temperature is 75 ℃.
The polybutadiene rubber synthesized by the process and the formula has the bimodal molecular weight of 119kg/mol and 476kg/mol, the light transmittance of 89% of the high-gloss transparent ABS resin, the impact strength of 12.2kJ/m 2 and the glossiness of 107.8GU under a 60-degree test angle.
Comparative example 1
According to Chinese patent application (publication number: CN 114921050B)' A modified ABS resin, preparation method thereof, modified ABS composite material and application thereof
S1, soaking layered silicate in a NaOH solution with the concentration of 1.5mol/L, heating to 40 ℃ for 1 hour, filtering, and washing to obtain pretreated layered silicate;
S2, dissolving 7g of sulfanilic acid in 100mL of water, adding 50g of the pretreated layered silicate prepared in the step S1, regulating the pH value of the solution to 8.5, heating to 50 ℃ for reaction for 2 hours, filtering, washing and drying to obtain sulfanilic acid intercalated layered silicate;
S3, adding 100g of the sulfanilic acid intercalation layered silicate prepared in the step S2 into 50wt% ethanol solution, adding 5g of silane coupling agent A151, heating to 70 ℃ for reaction for 1h, filtering, washing and drying to obtain modified layered silicate;
S4, uniformly mixing 7g of the modified phyllosilicate prepared in the step S3, 0.5g of ammonium persulfate and 100g of ABS resin, carrying out melt reaction at 180 ℃ for 0.5h, and carrying out extrusion granulation to obtain the modified ABS resin with the impact property of 10.7kJ/m 2.
Comparative example 2
According to Chinese patent application (publication No. CN 115785609B)' A transparent ABS resin composition, its preparation method and application
Provided are a transparent ABS resin composition and a method for preparing the same, wherein the transparent ABS resin composition comprises the following raw materials in percentage by mass: 99.33% of acrylonitrile-butadiene-styrene copolymer, 0.06% of methyl methacrylate-butadiene-styrene copolymer, 0.06% of pentaerythritol, 0.5% of diphenyl dimethoxy silane and 0.05% of nano platinum;
The preparation method of the transparent ABS resin composition comprises the following steps: uniformly mixing the powder granular methyl methacrylate-butadiene-styrene copolymer and a nano platinum solution (the addition mass of the nano platinum solution is 2.5 times of the total mass of the transparent ABS resin composition), and drying to form an intermediate of the nano platinum attached to the powder granular methyl methacrylate-butadiene-styrene copolymer; mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying at 60 ℃; then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and adopting a double-screw extruder to melt and extrude to obtain the transparent ABS resin composition, wherein the screw speed of the double-screw extruder is 220r/min, and the working temperature of the double-screw extruder is as follows: a region: 200 ℃; two areas: 205 deg.c; three regions: 210 ℃; four regions: 215 ℃; five regions: 215 ℃; six areas: 215 ℃; and (3) a die head: 205 ℃. The prepared ABS resin has light transmittance of 86% and impact strength of 11kJ/m 2.
Comparative example 3
According to Chinese patent application (publication number: CN 112375330B)' A high-gloss hydrophobic ABS composition, and preparation method and application thereof
The high-gloss hydrophobic ABS composition is prepared from the following raw materials in parts by weight: 92 parts of ABS, 1 part of a hydrophobic auxiliary agent, 2 parts of a compatilizer, 5 parts of a brightening agent, 0.4 part of an antioxidant and 0.2 part of a lubricant.
The hydrophobic auxiliary agent is prepared by a method comprising the following steps: adding absolute ethyl alcohol into the polymer fluoride, uniformly mixing, grinding for 5min at 2000r/min, filtering out precipitate, drying the precipitate, mixing the precipitate with an equal amount of ABS resin, and extruding and granulating by a double-screw extruder to obtain the modified polymer fluoride.
The preparation method of the high-gloss hydrophobic ABS composition comprises the following steps: uniformly mixing the raw materials, feeding the raw materials from a main feeding port of an extruder, and obtaining the high-gloss hydrophobic ABS composition after melting, extruding and granulating the raw materials in the extruder; the extruder is a double-screw extruder; the processing conditions of the extruder melt extrusion are as follows: the temperature of the first area is 100-120 ℃, the temperature of the second area is 160-180 ℃, the temperature of the third area is 180-200 ℃, the temperature of the fourth area is 180-200 ℃, the temperature of the fifth area is 190-210 ℃, the temperature of the sixth area is 190-210 ℃, the temperature of the seventh area is 200-220 ℃, the temperature of the eighth area is 200-220 ℃, the temperature of the ninth area is 210-230 ℃ and the rotating speed of the host is 300-600 revolutions per minute. The prepared ABS resin has a gloss of 92GU at a test angle of 60 degrees.
Comparative example 4 (reduction of coupling agent)
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 240 parts of cyclohexane, 30 parts of butadiene, 0.002 part of tetrahydrofuran, 0.2 part of n-butyllithium, 0.002 part of silicon tetrachloride and 0.10 part of isopropanol. The reaction temperature was 50℃and the stirring rate was 150r/min. The initiator and modifier are added and reacted for 1 hour, and then the coupling agent is added and reacted for 2 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 40 parts of styrene, 5 parts of star-shaped polybutadiene rubber, 10 parts of acrylonitrile and 20 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 20 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00002 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00005 part, and the nitrogen purging time is 30 minutes.
The stirring speed of the step (5) is 600r/min, and the reaction temperature is 140 ℃. The reaction time was 8 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 12 hours, the drying time is 48 hours, and the drying temperature is 80 ℃.
The polybutadiene rubber synthesized by the process and the formula has the bimodal molecular weight of 102kg/mol and 407kg/mol, wherein the content of the coupling rubber is small, the performance of the high-gloss transparent ABS resin is reduced, the light transmittance is 86%, the impact strength is 10.3kJ/m 2, and the glossiness is 75.8GU under a 60-degree test angle.
Comparative example 5 (increasing initiator and decreasing coupling agent)
A preparation method of transparent ABS resin comprises the following steps:
(1) Removing polymerization inhibitor from styrene, methyl methacrylate and acrylonitrile with alkaline alumina, and strictly removing water and oxygen from butadiene storage tank, cyclohexane storage tank, tetrahydrofuran and isopropanol.
(2) Introducing cyclohexane and butadiene into a reaction kettle, setting the temperature and stirring speed, pumping an alkyl lithium initiator and a modifier tetrahydrofuran, then adding a coupling agent, and stopping the reaction by using isopropanol after the reaction reaches the end.
(3) Mixing and dissolving the prepared star polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and solvent with polymerization inhibitor removed.
(4) Pouring the dissolved glue solution, the free radical initiator and the chain transfer agent into a reactor for nitrogen purging.
(5) Covering the reactor, starting stirring, starting heating, dissolving the polymer after reacting for a certain time, using a poor solvent for gum precipitation, shearing the precipitated polymer, and drying at a certain temperature in a vacuum environment.
And (3) removing all polymerization inhibitors in the step (1) by using an alkaline alumina chromatographic column.
The initiator in the step (2) is n-butyllithium, the coupling agent is silicon tetrachloride, and all the raw materials in the step (2) are proportioned according to the following parts by weight: 240 parts of cyclohexane, 30 parts of butadiene, 0.002 part of tetrahydrofuran, 0.4 part of n-butyllithium, 0.002 part of silicon tetrachloride and 0.10 part of isopropanol. The reaction temperature was 50℃and the stirring rate was 150r/min. The initiator and modifier are added and reacted for 1 hour, and then the coupling agent is added and reacted for 2 hours.
All the raw materials in the step (3) and the step (4) are proportioned according to the following parts by weight: 40 parts of styrene, 5 parts of star-shaped polybutadiene rubber, 10 parts of acrylonitrile and 20 parts of methyl methacrylate, wherein the solvent is ethylbenzene, the solvent addition amount is 20 parts, the initiator is di-tert-butyl peroxide, the addition amount is 0.00002 part, the chain transfer agent is tert-dodecyl mercaptan, the addition amount of the chain transfer agent is 0.00005 part, and the nitrogen purging time is 30 minutes.
The stirring speed of the step (5) is 600r/min, and the reaction temperature is 140 ℃. The reaction time was 8 hours. The poor solvent is methanol, and the solvent used for dissolving the polymer is dichloromethane. The glue depositing time is 12 hours, the drying time is 48 hours, and the drying temperature is 80 ℃.
The polybutadiene rubber synthesized by the process and the formula has the bimodal molecular weight of 46kg/mol and 176kg/mol, wherein the rubber has low molecular weight and low coupling rubber content, the performance of the high-gloss transparent ABS resin is reduced, the light transmittance of the high-gloss transparent ABS resin is 87%, the impact strength is 10.0kJ/m 2, and the glossiness is 69.1GU under a 60-degree test angle.
Examples 1-4 were compared with comparative example 1 for impact strength, example 1 for impact strength of 12.4kJ/m 2, example 2 for impact strength of 11.7kJ/m 2, example 3 for impact strength of 11.3kJ/m 2, example 4 for impact strength of 11.8kJ/m 2, and comparative example 1 for impact performance of 10.7kJ/m 2. From the data, the star-shaped low cis-polybutadiene rubber toughened transparent ABS resin synthesized herein has excellent impact resistance.
The light transmittance and impact strength of examples 1-4 were compared with those of comparative example 2, the light transmittance of example 1 was 87%, and the impact strength was 12.4kJ/m 2; example 2 has a light transmittance of 88% and an impact strength of 11.7kJ/m 2; example 3 has a light transmittance of 89% and an impact strength of 11.3kJ/m 2; example 4 has a light transmittance of 88% and an impact strength of 11.8kJ/m 2; the light transmittance of comparative example 2 was 86% and the impact strength was 11kJ/m 2, so that the transparent ABS resin excellent in transparency and impact resistance was prepared according to the present invention.
Comparing example 8 with comparative examples 4 and 5, the gloss values of example 8, comparative example 4 and comparative example 5 were 97.9GU, 75.8GU, 72.1GU, respectively, indicating that toughening the ABS resin in the same manner after changing the rubber formulation did not result in a high gloss ABS resin.
The ABS resins of examples 1 to 9 had gloss values of 102.6GU, 103.6GU, 96.9GU, 102.2GU, 103.3GU, 108.8GU, 102.6GU, 97.9GU, 107.8GU in this order at a test angle of60℃whereas the ABS resin of comparative example 3 had a gloss value of 92GU at 60℃and the sample of the example had a higher gloss value than the sample of the comparative example, so that the ABS resin prepared by the present invention was a high-gloss transparent ABS resin.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The high-gloss transparent ABS resin is characterized by comprising the following components in parts by weight:
40-60 parts of styrene, 5-20 parts of star-shaped low cis-polybutadiene rubber, 10-20 parts of acrylonitrile and 20-40 parts of methyl methacrylate; the molecular weight of the star-shaped low cis-polybutadiene rubber is 100-600kg/mol;
The prepared high-gloss transparent ABS resin has the molecular weight of 70-200kg/mol, the light transmittance of 85-90% and the glossiness (60 ℃) of 96-109GU.
2. The high-gloss transparent ABS resin according to claim 1, wherein the resin comprises, by mass, 45 to 55 parts of styrene, 10 to 15 parts of star-shaped low cis-polybutadiene rubber, 13 to 15 parts of acrylonitrile, and 25 to 35 parts of methyl methacrylate.
3. A method for preparing a high-gloss transparent ABS resin according to any one of claims 1 to 2, comprising the steps of:
S1, mixing and dissolving star-shaped low cis-polybutadiene rubber, styrene, methyl methacrylate, acrylonitrile and a solvent to obtain a mixed solution;
s2, adding the mixed solution, a free radical initiator and a chain transfer agent into a reactor;
s3, after oxygen is discharged, stirring and heating are started, and after a certain time of reaction, the polymer is dissolved, glue is deposited, broken and dried, so that the high-gloss transparent ABS resin is obtained.
4. The preparation method according to claim 1, wherein the star-shaped low cis-polybutadiene rubber is prepared by the following method: introducing cyclohexane and butadiene into a reaction kettle, wherein the reaction temperature is 50-60 ℃, the stirring speed is 150-200r/min, and adding an alkyl lithium initiator and tetrahydrofuran for reaction for 1-2 hours; and adding a coupling agent, reacting for 2-2.5 hours, and adding isopropanol to terminate the reaction to obtain the star-shaped low cis-polybutadiene rubber.
5. The preparation method of claim 4, wherein the raw material components are mixed according to the following parts by weight: 220-240 parts of cyclohexane, 25-30 parts of butadiene, 0.001-0.002 part of tetrahydrofuran, 0.1-0.2 part of alkyl lithium, 0.02-0.075 part of coupling agent and 0.09-0.10 part of isopropanol.
6. The method of preparing as claimed in claim 4, wherein the coupling agent is selected from silicon tetrachloride.
7. The preparation method according to claim 3, wherein the raw materials are mixed according to the following parts by weight: 40-60 parts of styrene, 5-20 parts of star-shaped low cis-polybutadiene rubber, 10-20 parts of acrylonitrile and 20-40 parts of methyl methacrylate; the addition amount of the free radical initiator is 0.00002-0.00005 part; the addition amount of the chain transfer agent is 0.00005-0.00015 part; the solvent is added in an amount of 20-30 parts.
8. The process of claim 7 wherein the free radical initiator is di-t-butyl peroxide; the chain transfer agent is at least one of n-dodecyl mercaptan and tert-dodecyl mercaptan; the solvent is at least one of ethylbenzene and xylene.
9. The preparation method according to claim 3, wherein the stirring rate in the step S3 is 180-600r/min, and the reaction temperature is 100-140 ℃; the reaction time is 4-8 hours.
10. A process according to claim 3, wherein the polymerization inhibitor is removed from the raw materials of styrene, methyl methacrylate and acrylonitrile by basic alumina before use; and (3) removing water and oxygen from the butadiene storage tank, the cyclohexane storage tank, the tetrahydrofuran and the isopropanol.
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