CN113667255A - Spraying-free PMMA alloy material with high appearance performance and preparation method thereof - Google Patents
Spraying-free PMMA alloy material with high appearance performance and preparation method thereof Download PDFInfo
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- CN113667255A CN113667255A CN202110909920.5A CN202110909920A CN113667255A CN 113667255 A CN113667255 A CN 113667255A CN 202110909920 A CN202110909920 A CN 202110909920A CN 113667255 A CN113667255 A CN 113667255A
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 62
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 62
- 239000000956 alloy Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000010445 mica Substances 0.000 claims abstract description 30
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 30
- 239000000049 pigment Substances 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 25
- 230000000694 effects Effects 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 229920001897 terpolymer Polymers 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000007822 coupling agent Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000001023 inorganic pigment Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 6
- 238000004873 anchoring Methods 0.000 claims description 5
- -1 titanium dioxide metal oxides Chemical class 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 10
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- 238000012545 processing Methods 0.000 abstract description 5
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- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005805 hydroxylation reaction Methods 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract description 2
- 230000033444 hydroxylation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention relates to a high-appearance-performance spray-free PMMA alloy material, a preparation method and a preparation method thereof, and the spray-free PMMA alloy material is specifically composed of the following raw materials in parts by weight: 40-80 parts of PMMA resin, 10-25 parts of ASA terpolymer, 1-5 parts of mica pearlescent pigment, 0.5-3 parts of multifunctional auxiliary agent, 0.5-3 parts of high-performance silane coupling agent and 0.5-2 parts of grafting initiator. The invention has the beneficial effects that: through the high surface activity of the hydroxylation treatment on the surface of the mica pearl powder, the pearl powder is firmly anchored in a resin matrix through a chemical bonding effect in a double-screw extruder and a PMMA resin matrix through a chemical grafting reaction, so that the mobility of the pearl powder along with the processing migration of a resin melt during injection molding processing is greatly improved, and the phenomenon of sheet layer crushing caused by excessive shearing of a screw is avoided, thereby obtaining the high appearance performance of large particle size, strong pearl scintillation, no welding line and no gas mark, and simultaneously, the mechanical property of the PMMA alloy material is also improved to a certain degree.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-appearance spraying-free PMMA alloy material and a preparation method thereof.
Background
Due to the limitation of the material characteristics of the polymer material, the surface gloss formed by injection molding of the polymer material is often not high, and the color and pattern effects are very single, so in the traditional surface treatment process of shells and decorative parts in the fields of automobiles, household appliances, industrial electrical appliances and the like, the surface painting treatment is still the most common method at present for obtaining the special effects of high brightness, high gloss, multicolor, patterning and the like of injection molded parts, and therefore, a series of environmental protection and health problems are brought. Although some new paints such as water-based paints, primer-free paints, and the like have been developed in recent years, it is still difficult to cover the above-mentioned fields, particularly high-appearance, high-durability automobile parts.
The spraying-free polymer matrix composite is a new special functional material with high environmental protection, high appearance effect and low cost aiming at the difficulties, and the satisfactory appearance effect of a finished piece can be obtained after direct injection molding by adding some inorganic toner containing special components and structures, such as metallic toner, pearl powder, organic-inorganic hybrid toner and the like, into polymer matrix resin. However, due to the great performance difference between the polymer material and the inorganic pigment, the inorganic pigment cannot achieve ideal dispersion and distribution effects in a high-viscosity polymer resin matrix (such as Polycarbonate (PC), polymethyl methacrylate (PMMA), and the like), and after injection molding, appearance air marks and weld lines often appear, and the phenomena of small pearl particle size, weak scintillation effect, and the like are often caused.
In spite of the existing spray-free modification technology focusing on the compatibility of inorganic pigments, a simple coupling agent surface treatment method is mostly adopted to achieve the modification purpose, for example, the coupling agent and the inorganic pigments are added into a high-speed mixing roll in CN108276718A and stirred for a certain time, so that the purpose of surface compatibilization modification is achieved. Therefore, a technical scheme for modifying the spraying-free pigment based on chemical reaction grafting and with high anchoring effect has to be searched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a spraying-free PMMA alloy material with high appearance performance, aiming at the current situation that the compatibility modification scheme of the existing inorganic pigment is less and most of the inorganic pigment is concentrated on simple physical blending, inorganic pigment powder with high surface activity is obtained through the surface hydroxylation reaction between the inorganic pigment and a novel high-performance silane coupling agent, then the inorganic pigment powder and a PMMA resin matrix are subjected to a chemical grafting reaction initiated by Atom Transfer Radical Polymerization (ATRP), and the pearl powder with surface activity is anchored in the PMMA/ASA alloy resin matrix through a chemical bonding effect, so that the migration fluidity of the PMMA/ASA alloy resin matrix in injection molding processing is greatly improved, the phenomenon of sheet layer breakage caused by excessive shearing of a screw is avoided, and the high appearance performance of large particle size, strong pearl scintillation, no welding line and no gas mark is obtained.
The purpose of the invention is realized by the following technical scheme:
the high-appearance-performance spray-free PMMA alloy material comprises the following raw materials in parts by weight:
in the spray-free PMMA alloy material,
the PMMA resin is polymethyl methacrylate with high flow and high light transmittance, the melt index MFR of the PMMA resin is more than or equal to 15g/10min under the test conditions of 230 ℃ and 3.8kg, and the light transmittance is more than or equal to 93%.
The ASA terpolymer is high impact resistance ASA superfine powder resin with the acrylate rubber phase content of 45-50%, and the average particle size (D98) is 3-5 um.
The mica pearlescent pigment is a large-sheet layered inorganic pigment with a glittering appearance expression, wherein mica sheets are used as cores, and the surfaces of the mica pearlescent pigment are alternately coated with a plurality of layers of titanium dioxide metal oxides by an electrochemical deposition method.
The multifunctional additive is a multifunctional group structure polymer with a high-activity anchoring group, and has multiple auxiliary functions of dispersion, compatibility, coupling, lubrication and the like.
The high-performance silane coupling agent is a novel carboxylated silane coupling agent, and the molecular structure of the high-performance silane coupling agent has two functional groups, namely an organic plasticizing group and a high-steric-hindrance mercapto silane coupling group.
The grafting initiator is active organic compound 2-bromo isobutyryl bromide.
The second purpose of the invention is to provide a spraying-free PMMA alloy material with high appearance performance and a preparation method thereof, and the method is characterized by comprising the following steps:
(1) respectively weighing the mica pearlescent pigment and the high-performance coupling agent according to the weight parts, adding the pearlescent pigment into a glass container containing 60ml of high-concentration ethanol (90%), performing ultrasonic dispersion for 60min, adding the high-performance coupling agent, adjusting the water bath temperature to be 75 ℃, starting mechanical stirring, performing hydrolysis reaction for 2h to fully coat the coupling agent on the surface of the pigment lamellar structure, and then filtering and drying.
(2) Respectively weighing PMMA resin, ASA terpolymer and functional auxiliary agent according to the weight parts, uniformly mixing, placing into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding into a machine barrel of the extruder through a feeding screw; and pumping out the grafting initiator solution stored in a low-temperature environment through a high-precision liquid metering pump, and filling the grafting initiator solution into the machine barrel through a liquid feed port at the top of the second section of the machine barrel. The diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material with high appearance expression is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the main machine rotating speed of 200 r/min.
Compared with the prior art, the invention has the following beneficial effects:
1. firstly, different from the traditional scheme that simple physical blending and stirring are carried out only in a high-speed mixer, the scheme of the invention designs a specific inorganic pigment surface treatment link, and enables the high-performance high-steric-hindrance mercaptosilane coupling agent to be fully coated on the surface of large-sheet-shaped lamellar mica pearl powder through ultrasonic dispersion and long-time (2h) mechanical stirring, thereby providing good basic conditions for further subsequent dispersion, grafting, anchoring and extrusion in a PMMA resin matrix.
2. In the specific preparation link of the spray-free PMMA \ ASA alloy material, 2-bromoisobutyryl bromide with a specific chemical structure is used as an initiator, a metal oxide layer on the surface layer of the pearl powder is used as an initiator aid, and the pearl powder pigment subjected to surface organic treatment is fully anchored on a PMMA molecular branched chain structure by utilizing active Atom Transfer Radical Polymerization (ATRP), so that the processing fluidity and the final dispersion distribution effect of the mica pearl toner are remarkably improved, and the poor appearance phenomena such as weld lines, surface gas marks and the like caused by the orientation of mica sheets due to the fluidity difference are avoided.
3. The spraying-free PMMA alloy material with high appearance performance obtained by the technical scheme of the invention is used for improving the compatibility between inorganic phase pearlescent toner and PMMA \ ASA alloy resin, on one hand, the main mechanical property index of the alloy material can be comprehensively improved, the alloy material not only has higher tensile and bending strength performance, but also has more obvious improvement on the impact toughness, and the low temperature resistant (-30 ℃) notch impact strength is 9.3kJ/m before modification2Greatly increased to 15kJ/m2Left and right. More importantly, the chemical grafting method realizes the high-efficiency compatibilization technology, avoids the randomness and uncertainty of the melt flow of the pearlescent toner during the injection molding processing, and is beneficial to the regular orientation, arrangement and distribution of mica sheets,And distribution, in the verification of actual complex part injection molding (washing machine panel), excellent part appearance surface performances such as no weld line, no air mark, large particle size, strong pearl scintillation and the like are successfully realized.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
The raw materials used in the embodiment of the invention are as follows:
PMMA-1: polymethyl methacrylate IF870S, melt index MFR of 21g/10min at 230 ℃ under 3.8kg test conditions, 95% transmittance, Korean LG chemistry.
PMMA-2: polymethyl methacrylate HFI-10, melt index MFR of 15g/10min at 230 ℃ under 3.8kg, light transmittance 90%, Achima, France.
ASA terpolymer: the ultrafine acrylic resin powder S757G, which had an acrylic ester content of 47%, was a white powder having an average particle size (D98) of 2.5um, manufactured by BASF, Germany.
Mica pearlescent pigment-1: the natural MICA titanium pearl powder GLI-305L is yellow flashing gold, the content of natural MICA (MICA) is 35-43%, the content of titanium dioxide is 52-63%, the average particle size (D98) is 10-60um, and Jiangsu Beili new material company Limited.
Mica pearlescent pigment-2: the composite fluorophlogopite titanium pearl powder GLI-3310 is yellow flashing gold, the content of the composite fluorophlogopite is 46-67%, the content of titanium dioxide is 30-45%, the average particle size (D98) is 30-100um, and Jiangsu Beili new material company Limited.
Mica pearlescent pigment-3: the natural MICA iron pearl powder IRI-500, the bronze, the natural MICA (MICA) content is 61-65%, the ferric oxide content is 35-39%, the average particle size (D98) is 10-60um, and Jiangsu Beili obtains new material limited company.
Multifunctional auxiliary agent: the organic polar group grafted multifunctional polymer assistant YY-703 is white or yellowish powder, has a melting point of not less than 150 ℃, and is prepared by Guangzhou Yuntai synthetic materials Co.
High-performance silane coupling agent: hydroxylated silane coupling agent NTX, Ma-El-New materials, Inc., USA.
Grafting initiator: 2-bromo isobutyryl bromide, purity 99%, salt city cloud peak chemical company Limited.
And (3) product performance testing:
tensile property: the test was carried out at a test rate of 50mm/min at normal temperature (23 ℃) after injection molding of a standard specimen in accordance with the specimen size specified in ISO 527-2.
Bending property: according to the sample strip size specified by IS178, a standard sample strip IS injection-molded and then tested, the test span IS 64mm, the test speed IS 2mm/min, and the test IS carried out at the normal temperature (23 ℃).
Impact properties: according to the sample strip size specified by ISO179-1 standard, the test is carried out after the injection molding of a standard sample strip on a simply supported beam impact tester with the notch type of A, and the test is carried out at low temperature (-30 ℃).
And (3) testing the pearl effect: a standard sample plate of 160 multiplied by 120 multiplied by 3.2mm is injected and placed for 48 hours in a standard environment of 23 ℃ and 50 percent RH, then observed under a Leica DMi8 inverted metallographic microscope, and connected in parallel with Leica LASImage Analysis software to obtain the surface average grain size of the pearl powder.
And (3) part injection molding verification: and (3) injection molding parts on a washing machine panel mold, wherein the molding temperature is 210-230 ℃, the parts are placed in a standard environment with 23 ℃ and 50% RH for 48h, and then the conditions of the welding lines and the gas marks on the surfaces of the parts are observed in a standard inspection lamp box. .
Example 1
The mica pearlescent pigment and the high-performance coupling agent are weighed according to the data of example 1 shown in the table 1, the pearlescent pigment is added into a glass container containing 60ml of high-concentration ethanol (90 percent), ultrasonic dispersion is carried out for 60min, the high-performance coupling agent is added, the water bath temperature is adjusted to be 75 ℃, mechanical stirring is started, the hydrolysis reaction time is 2h, so that the coupling agent is fully coated on the surface of the pigment lamellar structure, and then filtration and drying are carried out.
Respectively weighing PMMA resin, ASA terpolymer and functional auxiliary agent according to the data of example 1 shown in Table 1, uniformly mixing, placing into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding into a machine barrel of the extruder through a feeding screw; and pumping out the grafting initiator solution stored in a low-temperature environment through a high-precision liquid metering pump, and filling the grafting initiator solution into the machine barrel through a liquid feed port at the top of the second section of the machine barrel. The diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material with high appearance expression is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the main machine rotating speed of 200 r/min.
Example 2
The mica pearlescent pigment and the high-performance coupling agent are weighed according to the data of example 2 shown in the table 1, the pearlescent pigment is added into a glass container containing 60ml of high-concentration ethanol (90 percent), ultrasonic dispersion is carried out for 60min, the high-performance coupling agent is added, the water bath temperature is adjusted to be 75 ℃, mechanical stirring is started, hydrolysis reaction time is 2h, so that the coupling agent is fully coated on the surface of the pigment lamellar structure, and then filtration and drying are carried out.
Respectively weighing PMMA resin, ASA terpolymer and functional auxiliary agent according to the data of example 1 shown in Table 1, uniformly mixing, placing into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding into a machine barrel of the extruder through a feeding screw; and pumping out the grafting initiator solution stored in a low-temperature environment through a high-precision liquid metering pump, and filling the grafting initiator solution into the machine barrel through a liquid feed port at the top of the second section of the machine barrel. The diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material with high appearance expression is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the main machine rotating speed of 200 r/min.
TABLE 1 high appearance no-spray PMMA alloy material formulation table (unit: gram)
Example 3
The mica pearlescent pigment and the high-performance coupling agent are weighed according to the data of example 3 shown in the table 1, the pearlescent pigment is added into a glass container containing 60ml of high-concentration ethanol (90 percent), ultrasonic dispersion is carried out for 60min, the high-performance coupling agent is added, the water bath temperature is adjusted to be 75 ℃, mechanical stirring is started, the hydrolysis reaction time is 2h, so that the coupling agent is fully coated on the surface of the pigment lamellar structure, and then filtration and drying are carried out.
Respectively weighing PMMA resin, ASA terpolymer and functional auxiliary agent according to the data of example 1 shown in Table 1, uniformly mixing, placing into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding into a machine barrel of the extruder through a feeding screw; and pumping out the grafting initiator solution stored in a low-temperature environment through a high-precision liquid metering pump, and filling the grafting initiator solution into the machine barrel through a liquid feed port at the top of the second section of the machine barrel. The diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material with high appearance expression is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the main machine rotating speed of 200 r/min.
Example 4
The mica pearlescent pigment and the high-performance coupling agent are weighed according to the data of example 4 shown in the table 1, the pearlescent pigment is added into a glass container containing 60ml of high-concentration ethanol (90 percent), ultrasonic dispersion is carried out for 60min, the high-performance coupling agent is added, the water bath temperature is adjusted to be 75 ℃, mechanical stirring is started, the hydrolysis reaction time is 2h, so that the coupling agent is fully coated on the surface of the pigment lamellar structure, and then filtration and drying are carried out.
Respectively weighing PMMA resin, ASA terpolymer and functional auxiliary agent according to the data of example 1 shown in Table 1, uniformly mixing, placing into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding into a machine barrel of the extruder through a feeding screw; and pumping out the grafting initiator solution stored in a low-temperature environment through a high-precision liquid metering pump, and filling the grafting initiator solution into the machine barrel through a liquid feed port at the top of the second section of the machine barrel. The diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material with high appearance expression is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the main machine rotating speed of 200 r/min.
Example 5
The mica pearlescent pigment and the high-performance coupling agent are weighed according to the data of example 5 shown in the table 1, the pearlescent pigment is added into a glass container containing 60ml of high-concentration ethanol (90 percent), ultrasonic dispersion is carried out for 60min, the high-performance coupling agent is added, the water bath temperature is adjusted to be 75 ℃, mechanical stirring is started, the hydrolysis reaction time is 2h, so that the coupling agent is fully coated on the surface of the pigment lamellar structure, and then filtration and drying are carried out.
Respectively weighing PMMA resin, ASA terpolymer and functional auxiliary agent according to the data of example 1 shown in Table 1, uniformly mixing, placing into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding into a machine barrel of the extruder through a feeding screw; and pumping out the grafting initiator solution stored in a low-temperature environment through a high-precision liquid metering pump, and filling the grafting initiator solution into the machine barrel through a liquid feed port at the top of the second section of the machine barrel. The diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material with high appearance expression is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the main machine rotating speed of 200 r/min.
Comparative example 1
Weighing PMMA resin, ASA resin and mica pearl powder pigment according to the data of the comparative example 1 shown in the table 1, and uniformly mixing to obtain mixed raw materials:
placing the dried mixed raw materials into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; the diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the rotating speed of a main engine of 200 r/min.
Comparative example 2
Spray-free PMMA/ASA alloy-HAM 8650, available from Shanghai brocade lake Nillie Co.
TABLE 2 test results of spray-free PMMA alloy materials with high appearance performance
The composition and test data of each example and comparative example in tables 1 and 2 show that the most critical influence factor for achieving the desired effect of the surface spray-free condition in the engineering plastic PMMA with high melt viscosity is the dispersion and distribution condition of the spray-free toner, which mainly depends on the chemical condition of the surface and the adhesion degree with PMMA matrix resin.
From the test data of comparative example 1, it can be seen that simply adding the spray-free toner (mica titanium pearl powder) not only has a low mechanical property, but also has an obvious surface weld line and a serious gas mark, which indicates that the added pearl powder is bound and anchored with the resin matrix gap; the commercial grade (comparative example 2) has not yet achieved the desired surface condition, although it has improved optimally. After the scheme of the toner organized surface treatment and the free radical chemical grafting anchoring, the dispersion and distribution conditions of the pearl powder are improved to different degrees, particularly, the improvement of the welding line is particularly obvious and can basically reach a slight grade, and the embodiment 5 can reach an ideal level without the welding line and the surface gas mark; further, it is understood from comparative examples 3, 4 and 5 that the effect of the metal oxide on the surface layer of the pearl powder on the graft reaction is not negligible, and the effect of the titanium dioxide layer (examples 4 and 5) is remarkable because it has a certain effect of promoting the initiation of the radical chemical graft reaction, and the effect of the titanium dioxide layer is remarkably attributed to the iron sesquioxide layer (example 3).
In addition, comparing the examples and the comparative examples, it can be seen that the spraying-free toner as an inorganic powder negatively affects the mechanical properties of PMMA alloy, especially the notch impact toughness, and the improvement of the adhesiveness with the matrix resin undoubtedly compensates for the toughness loss to some extent, and from the data of the notch impact toughness test at low temperature (-30 ℃), the examples 4 and 5 with good surface treatment effect and more thorough grafting reaction have the highest notch impact strength (15 kJ/m)2) The improvement compared to the data of comparative example 1 is nearly 60%.
The invention discloses a spraying-free PMMA alloy material with high appearance performance and a preparation method thereof, which are special-specification spraying-free materials specially developed aiming at the spraying-free design of parts with complex shapes and numerous reinforcing ribs in the fields of automotive upholsteries and household electronic appliances, and the good organic/inorganic two-phase interface adhesion of the spraying-free PMMA alloy material can completely meet the strict requirements of the technical trends of intellectualization, aesthetics, environmental protection and the like in the application field on the appearance of the spraying-free parts.
Claims (8)
1. The spraying-free PMMA alloy material with high appearance performance is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the high appearance spray-free PMMA alloy material of claim 1, which is characterized in that: the PMMA resin is polymethyl methacrylate with high flow and high light transmittance, the melt index MFR of the PMMA resin is more than or equal to 15g/10min under the test conditions of 230 ℃ and 3.8kg, and the light transmittance is more than or equal to 93%.
3. The high appearance spray-free PMMA alloy material of claim 1, which is characterized in that: the ASA terpolymer is high impact resistance ASA superfine powder resin with the acrylate rubber phase content of 45-50%, and the average particle size (D98) is 3-5 um.
4. The high appearance spray-free PMMA alloy material of claim 1, which is characterized in that: the mica pearlescent pigment is a large-sheet layered inorganic pigment with a glittering appearance expression, wherein mica sheets are used as cores, and the surfaces of the mica pearlescent pigment are alternately coated with a plurality of layers of titanium dioxide metal oxides by an electrochemical deposition method.
5. The high appearance spray-free PMMA alloy material of claim 1, which is characterized in that: the multifunctional additive is a multifunctional group structure polymer with a high-activity anchoring group, and has multiple auxiliary functions of dispersion, compatibility, coupling, lubrication and the like.
6. The high appearance spray-free PMMA alloy material of claim 1, which is characterized in that: the high-performance silane coupling agent is a novel carboxylated silane coupling agent, and the molecular structure of the high-performance silane coupling agent has two functional groups, namely an organic plasticizing group and a high-steric-hindrance mercapto silane coupling group.
7. The high appearance spray-free PMMA alloy material of claim 1, which is characterized in that: the grafting initiator is active organic compound 2-bromo isobutyryl bromide.
8. The method for preparing the high appearance spray-free PMMA alloy material according to any one of claims 1-7, which is characterized in that the method comprises the following steps:
(1) respectively weighing mica pearlescent pigment and high-performance coupling agent according to the weight parts, adding the pearlescent pigment into a glass container containing 60ml of high-concentration ethanol (90%), performing ultrasonic dispersion for 60min, adding the high-performance coupling agent, adjusting the water bath temperature to 75 ℃, starting mechanical stirring, performing hydrolysis reaction for 2h to fully coat the coupling agent on the surface of the pigment lamellar structure, and then filtering and drying;
(2) respectively weighing PMMA resin, ASA terpolymer and multifunctional auxiliary agent according to the weight parts, uniformly mixing, placing into a main feeding bin of a double-screw extruder which is tightly meshed and rotates in the same direction, and adding into a machine barrel of the extruder through a feeding screw; pumping out the grafting initiator solution stored in a low-temperature environment through a high-precision liquid metering pump, and filling the solution into the machine barrel through a liquid feed port at the top of the second section of machine barrel; the diameter of the screw extruder used was 30mm, the length-diameter ratio L/D was 48, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: the spraying-free PMMA alloy material with high appearance expression is obtained after the processes of melt extrusion, granulation, drying and the like are carried out at the temperature of 180 ℃, 220 ℃, 230 ℃, 220 ℃, 225 ℃, 220 ℃, 230 ℃ and the main machine rotating speed of 200 r/min.
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| WO2023174010A1 (en) * | 2022-03-18 | 2023-09-21 | 金发科技股份有限公司 | Spraying-free effect pigment, preparation method therefor and application thereof |
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