CN113583397A - Shading master batch based on low titanium dioxide content and preparation method thereof - Google Patents
Shading master batch based on low titanium dioxide content and preparation method thereof Download PDFInfo
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- CN113583397A CN113583397A CN202110807201.2A CN202110807201A CN113583397A CN 113583397 A CN113583397 A CN 113583397A CN 202110807201 A CN202110807201 A CN 202110807201A CN 113583397 A CN113583397 A CN 113583397A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 56
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 3
- 230000000475 sunscreen effect Effects 0.000 claims 1
- 239000000516 sunscreening agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000005022 packaging material Substances 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 44
- 239000005020 polyethylene terephthalate Substances 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 235000013365 dairy product Nutrition 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229930002330 retinoic acid Natural products 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229960001727 tretinoin Drugs 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 235000008924 yoghurt drink Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a shading master batch based on low titanium dioxide content, which is prepared from the following raw materials in parts by weight: 55-70 parts of PET resin, 15-25 parts of titanium dioxide, 10-20 parts of functional resin, 1-3 parts of organic silicon and 1-2 parts of graphite powder; wherein the functional resin is an olefin copolymer with a large side chain group. The invention also provides a preparation method of the shading master batch based on low titanium dioxide content. The PET packaging material prepared from the shading master batch disclosed by the invention has the advantages that the shading effect is ensured, the content of titanium dioxide is reduced, and the recycling value of PET bottles is improved.
Description
Technical Field
The invention relates to the technical field of food packaging materials, and particularly relates to a shading master batch based on low titanium dioxide content and a preparation method thereof.
Background
Dairy products are an important part of the daily diet, and their safety and nutritional maintenance are very important. Light irradiation causes rapid degradation of nutrients in dairy products, such as vitamin a, D and retinoic acid, and sometimes even at a loss rate of 51%.
Aiming at the problems, the package material manufacturers at home and abroad adopt various means to effectively store the dairy products, one means is to add titanium dioxide into a PET bottle and realize the shading effect by utilizing the blocking effect of the titanium dioxide on light, the effect score is obvious, the normal shading effect can reach more than 99 percent by the method, and even some manufacturers can reach more than 99.9 percent. The first step of the method is to prepare the titanium dioxide master batch with high ash content, wherein the content of titanium dioxide can reach 60-70%, and the addition amount of the master batch in the mixed material reaches 10-12%, so that the content of titanium dioxide in the bottle body finally reaches about 7%. And the high-content titanium dioxide can reduce the purity of PET, thereby causing great influence on the recycling of PET bottles and directly reducing the recycling value of the PET bottles.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the shading master batch based on low titanium dioxide content, and the PET packaging material prepared from the shading master batch reduces the titanium dioxide content and improves the recycling value of PET bottles while ensuring the shading effect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a shading master batch based on low titanium dioxide content is prepared from the following raw materials in parts by weight: 55-70 parts of PET resin, 15-25 parts of titanium dioxide, 10-20 parts of functional resin, 1-3 parts of organic silicon and 1-2 parts of graphite powder;
wherein the functional resin is an olefin copolymer with a large side chain group.
Preferably, the functional resin is a copolymer of propylene and 4-methyl-1-pentene, and has a melting point of 232 ℃ and a refractive index of 1.462.
Preferably, the PET resin is bottle grade polyester chip, and the intrinsic viscosity is 0.6-0.9 d/g.
Preferably, the titanium dioxide is rutile type, presents a blue phase, has a purity of more than or equal to 98 percent and has an average particle size of 0.23 mu m.
Preferably, the silicone is a silane coupling agent.
Preferably, the particle size of the graphite powder is 0.2-0.3 μm.
The invention also aims to provide a preparation method of the shading master batch based on low titanium dioxide content, which comprises the following steps:
weighing the materials according to a proportion, feeding the weighed PET resin and the weighed functional resin respectively through a weightless scale, and granulating through a double-screw extruder to obtain a component A;
mixing the weighed titanium dioxide and the weighed organic silicon at a high speed, standing to obtain a mixture, adding graphite powder into the mixture, and continuously mixing at a medium speed to obtain a component B;
feeding the component A and the component B into a double-screw extruder for granulation by a weightlessness scale to prepare the shading master batch.
Preferably, the twin-screw extruder adopts a screw combination mode, wherein the mode of dispersing mixing is taken as the main mode and the mode of distributing mixing is taken as the auxiliary mode.
Preferably, the twin-screw extruder process for preparing component A is as follows: the rotating speed of the screw is 310rpm, the yield is 150kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 235 ℃, temperature zone 3 is 235 ℃, temperature zone 4 is 235 ℃, temperature zone 5 is 235 ℃, temperature zone 6 is 235 ℃, temperature zone 7 is 235 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 225 ℃, temperature zone 12 is 225 DEG C
Preferably, the conditions during the preparation of component B are as follows: mixing at high speed of 1500rpm for 5min, standing for 30-40min, and mixing at medium speed of 800rpm for 8 min.
Preferably, the process of the double-screw extruder for preparing the shading master batch comprises the following steps: the rotating speed of the screw is 270rpm, the yield is 110kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 230 ℃, temperature zone 3 is 230 ℃, temperature zone 4 is 230 ℃, temperature zone 5 is 230 ℃, temperature zone 6 is 230 ℃, temperature zone 7 is 230 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 220 ℃ and temperature zone 12 is 220 ℃.
The invention has the beneficial effects that:
1. the shading master batch of the invention ensures that the functional resin is extremely small particles and uniformly dispersed in the PET resin by utilizing the incompatibility of the functional resin and the PET matrix, so that in the process of blow molding of a bottle blank, the functional resin and the PET resin are separated to form micropores along with the stretching of the PET resin under the control of a specific temperature zone, the whole PET bottle body has enough micropores, when light is irradiated, the light transmission of the PET bottle body is reduced due to the mutual great difference of the refractive indexes of the PET resin, air and the functional resin, the light refraction and scattering of every two interfaces cause the light to hardly transmit the bottle body, and the uniformly dispersed titanium dioxide has synergistic effect, thereby playing the role of shading, and the melting points of the functional resin and the PET resin are close to be more beneficial to molding processing; meanwhile, organic silicon in the components can be attached to titanium dioxide, polar groups in organic silicon molecules are compatible with PET in a reaction mode, and the compatibility of the titanium dioxide and a PET resin matrix is improved, so that the physical property of PET is reserved to the greatest extent, and the mechanical property of subsequent products is guaranteed; the graphite powder enhances the internal lubricating effect of the mixture system, further accelerates the dispersion rate and effect of titanium dioxide in the system, has a certain shading effect, plays a role in heat absorption and heat conduction in the blow molding process of the bottle preform, is beneficial to rapidly heating the bottle preform, has smaller temperature difference between the inside and the outside of the bottle preform and improves the production efficiency; therefore, the low-content titanium dioxide is cooperated with the functional resin and is supplemented with other additives, so that the shading effect of the shading master batch in the mixed material is ensured, the shading master batch is added into the bottle body in the same proportion of 10%, but the final content of the titanium dioxide is only 2-3%, the shading effect can reach more than 99.9%, and the low-content titanium dioxide and the simple components in the shading master batch improve the recovery value of the subsequent PET bottle while reducing the cost.
2. The invention mixes and granulates PET resin and functional resin by a step-by-step material mixing mode, mixes the mixture of titanium dioxide and organic silicon with graphite powder, and finally extrudes and granulates the premixed material, so that the material is uniformly fed in the continuous production process by the step-by-step material mixing mode; and the screw combination adopted by the double-screw extruder mainly adopts dispersion mixing and assists in distribution mixing, the dispersion mixing breaks the functional resin aggregate in a molten state into particles as small as possible, the particles are uniformly dispersed in the PET resin matrix after the distribution mixing, and the tiny particles in the PET resin are uniformly dispersed, and the uniformity of the material during subsequent granulation is ensured.
Detailed Description
In order to better understand the technical content of the invention, specific embodiments are described below.
It should be appreciated that the following embodiments may be implemented in any of numerous ways.
The invention provides a shading master batch based on low titanium dioxide content, which is characterized in that functional resin is enabled to be tiny particles and to be uniformly dispersed in PET resin by utilizing incompatibility of the functional resin and a PET matrix, so that in the process of blow molding of a bottle blank, the functional resin particles can form micropores due to stretching, and enough micropores exist in the whole bottle body, so that light is refracted and scattered and are supplemented with other components, the shading effect is ensured, the content of titanium dioxide is reduced, and the recycling value of a PET bottle is improved.
In a specific embodiment, the shading master batch is prepared from the following raw materials in parts by weight: 55-70 parts of PET resin, 15-25 parts of titanium dioxide, 10-20 parts of functional resin, 1-3 parts of organic silicon and 1-2 parts of graphite powder;
wherein the functional resin is an olefin copolymer with a large side chain group.
In a preferred embodiment, the functional resin is a copolymer of propylene and 4-methyl-1-pentene, having a melting point of 232 ℃ and a refractive index of 1.462.
It should be understood that the functional resin includes, but is not limited to, the above materials, and only the following conditions are satisfied: 1. the refractive index difference between the PET resin and the air is obvious, so that the light refraction and the light scattering are facilitated, and the transparency of the PET bottle body is reduced; 2. The melting temperature is close to that of PET resin, so that the degradation of low-melting-point materials caused by processing due to large melting point difference is avoided; 3. the elongation at break is low, which is beneficial to the micro-dispersion of materials and the formation of micropores; 4. is a non-polar material and is a polar incompatible material with PET resin products.
In other preferred embodiments, the PET resin is a bottle grade polyester chip with narrow molecular weight distribution and stable intrinsic viscosity, and the intrinsic viscosity is 0.6-0.9 d/g.
The titanium dioxide is rutile type, is blue phase, has the purity of more than or equal to 98 percent and has the average grain diameter of 0.23 mu m.
The silicone is a silane coupling agent in which the organic functional group is polar, reactive or compatible with PET, preferably methacryloxy silane.
The particle size of the graphite powder is 0.2-0.3 μm.
The invention also aims to provide a preparation method of the shading master batch based on low titanium dioxide content, which comprises the following steps:
weighing the materials according to the proportion, feeding the weighed PET resin and the weighed functional resin respectively through a weightless scale, and granulating through a double-screw extruder to obtain the component A.
And (3) mixing the weighed titanium dioxide and the weighed organic silicon at a high speed, standing to obtain a mixture, adding graphite powder into the mixture, and continuously mixing at a medium speed to obtain the component B.
Feeding the component A and the component B into a double-screw extruder for granulation by a weightlessness scale to prepare the shading master batch.
In a preferred embodiment, the twin-screw extruder adopts a screw combination, and adopts a mode of mainly dispersing and mixing and secondarily distributing and mixing; it is to be understood that dispersive mixing, i.e. breaking up large aggregates into many smaller aggregates, distributive mixing, i.e. mixing the different components (e.g. three components 1, 2, 3) more evenly, occurs in a twin screw extruder in both ways, except that the cohesive masses in the screw combination are different, with dispersive mixing being dominant and distributive mixing being the additional mixing.
In one embodiment, the twin screw extruder process for preparing component a is: the rotating speed of the screw is 310rpm, the yield is 150kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 235 ℃, temperature zone 3 is 235 ℃, temperature zone 4 is 235 ℃, temperature zone 5 is 235 ℃, temperature zone 6 is 235 ℃, temperature zone 7 is 235 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 225 ℃, temperature zone 12 is 225 DEG C
In another preferred embodiment, the conditions during the preparation of component B are as follows: mixing at high speed of 1500rpm for 5min, standing for 30-40min, and mixing at medium speed of 800rpm for 8 min.
In another embodiment, the process of the twin-screw extruder for preparing the light-shielding master batch comprises the following steps: the rotating speed of the screw is 270rpm, the yield is 110kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 230 ℃, temperature zone 3 is 230 ℃, temperature zone 4 is 230 ℃, temperature zone 5 is 230 ℃, temperature zone 6 is 230 ℃, temperature zone 7 is 230 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 220 ℃ and temperature zone 12 is 220 ℃.
The above preparation process and the prepared light-shielding mother particle are subjected to experimental tests in combination with specific examples below.
The experimental procedures used in the following examples and comparative examples are conventional ones unless otherwise specified. Materials, reagents, and the like used in the following embodiments are commercially available unless otherwise specified.
The following examples and comparative examples used the following starting materials:
PET resin: bottle grade slices, intrinsic viscosity 0.87dL/g, melting point 237 ℃; titanium dioxide: rutile type, blue phase, purity greater than or equal to 98%, average particle size 0.23 μm; organosilicon: a silane coupling agent, specifically methacryloxy silane; functional resin: olefin copolymers having large side chain groups, such as copolymers of propylene and 4-methyl-1-pentene, melting point 232 ℃, refractive index 1.462; graphite powder: the grain diameter is 0.2-0.3 μm;
and the preparation method of each embodiment is as follows:
1. and weighing the materials according to the proportion.
2. Feeding PET resin and functional resin by weight loss scales respectively, and granulating by a double-screw extruder to obtain a component A; wherein, the double-screw extruder comprises the following processes: the rotating speed of the screw is 310rpm, the yield is 150kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 235 ℃, temperature zone 3 is 235 ℃, temperature zone 4 is 235 ℃, temperature zone 5 is 235 ℃, temperature zone 6 is 235 ℃, temperature zone 7 is 235 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 225 ℃ and temperature zone 12 is 225 ℃.
3. Mixing titanium dioxide and organic silicon in a high-speed mixer for 5min, and standing for 30 min.
4. Adding graphite powder into the step 3, and continuously stirring at medium speed for 8min to obtain a component B.
5. Feeding the component A and the component B according to the mass ratio by a weightlessness scale, and granulating by a double-screw extruder to obtain final shading master batches; the process of the double-screw extruder comprises the following steps: the rotating speed of the screw is 270rpm, the yield is 110kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 230 ℃, temperature zone 3 is 230 ℃, temperature zone 4 is 230 ℃, temperature zone 5 is 230 ℃, temperature zone 6 is 230 ℃, temperature zone 7 is 230 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 220 ℃ and temperature zone 12 is 220 ℃.
The comparative example was prepared in the same manner as the examples except that comparative example 1 did not add the functional resin and comparative example 2 did not add titanium dioxide and silicone.
The component ratios of the examples and comparative examples are shown in table 1.
| Raw material components | PET resin | Titanium dioxide | Functional resin | Silicone | Graphite powder |
| Example 1 | 67 | 15 | 15 | 1 | 2 |
| Example 2 | 70 | 17 | 10 | 2 | 1 |
| Example 3 | 55 | 25 | 17 | 1.5 | 1.5 |
| Example 4 | 57 | 20 | 20 | 1.3 | 1.7 |
| Example 5 | 62 | 22 | 13 | 1.8 | 1.2 |
| Comparative example 1 | 81.4 | 15 | / | 1.2 | 2.4 |
| Comparative example 2 | 82.4 | / | 15 | / | 2.5 |
In comparative examples 1 and 2, the amount of the PET resin is increased to ensure that the percentage of the titanium dioxide or the functional resin in the whole material is fixed, so that the comparison is significant.
[ TEST ]
The samples of examples 1-5 and comparative examples 1-2 were tested, and the performance tests during the testing are illustrated below:
1. detection data are detection sample bars which are formed by adding 10% of the shading master batch prepared by the invention into PET resin particles, uniformly mixing and injection molding by using an injection molding machine;
2. the tensile property is performed by adopting a tensile sample strip with the thickness of 2mm, under the condition of the thickness, the pure PET resin sample strip can be transparent, and because the thickness of the sample strip is large, the middle part of the sample strip can be crystallized and non-transparent, the sample strip with the thickness of 2mm can prevent the influence of the difference of internal and external crystals on the mechanical property;
3. the tensile property is measured under the condition of maintaining 60s at 130 ℃, the temperature condition in the bottle blank blowing process can be simulated to the maximum extent under the condition, and the detection standard is according to ISO 527.
4. The light transmittance is detected by using an ASTM D1003 method; the master batch is added into PET (polyethylene terephthalate) by 10 percent, is molded into a bottle blank by injection and then is molded into a bottle by blow molding, and a relatively gentle area in a bottle body is intercepted to be a detection sample; the adopted packaging bottle model is a certain yoghurt drink packaging bottle sold in the market.
The performance ratios of examples 1-4 and comparative examples 1-6 are as follows:
from examples 1-5, it can be seen that the light-shielding master batch prepared by the invention can meet the requirement of elongation of the material in the bottle blowing process on the premise of adding 10% of the content, and the final light-shielding rate can reach more than 99.7%. Meanwhile, on the premise of adding 10% of the additive amount, the content of the titanium dioxide in the final packaging bottle is not more than 2.5%, which is beneficial to the recovery of PET bottles.
From the example 1, the comparative example 1 and the comparative example 2, it can be seen that the titanium dioxide and the functional resin play a critical role in shading effect, and the synergistic effect of the titanium dioxide and the functional resin is better.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (11)
1. The shading master batch based on low titanium dioxide content is characterized by comprising the following raw materials in parts by weight: 55-70 parts of PET resin, 15-25 parts of titanium dioxide, 10-20 parts of functional resin, 1-3 parts of organic silicon and 1-2 parts of graphite powder;
wherein the functional resin is an olefin copolymer with a large side chain group.
2. The shading master batch based on low titanium dioxide content according to claim 1, wherein the functional resin is a copolymer of propylene and 4-methyl-1-pentene, the melting point is 232 ℃, and the refractive index is 1.462.
3. The light-shielding master batch based on low titanium dioxide content according to claim 1, wherein the PET resin is bottle grade polyester chip and has an intrinsic viscosity of 0.6-0.9 d/g.
4. The light-shielding master batch based on the low titanium dioxide content according to claim 1, wherein the titanium dioxide is rutile type, is in a blue phase, has a purity of not less than 98%, and has an average particle size of 0.23 μm.
5. The low titanium dioxide content-based sunscreen masterbatch according to claim 1, wherein the silicone is a silane coupling agent.
6. The shading master batch based on low titanium dioxide content according to claim 1, wherein the graphite powder has a particle size of 0.2-0.3 μm.
7. The preparation method of the shading master batch based on low titanium dioxide content according to any one of claims 1 to 8, which is characterized by comprising the following steps:
weighing the materials according to a proportion, feeding the weighed PET resin and the weighed functional resin respectively through a weightless scale, and granulating through a double-screw extruder to obtain a component A;
mixing the weighed titanium dioxide and the weighed organic silicon at a high speed, standing to obtain a mixture, adding graphite powder into the mixture, and continuously mixing at a medium speed to obtain a component B;
feeding the component A and the component B into a double-screw extruder for granulation by a weightlessness scale to prepare the shading master batch.
8. The preparation method of the shading master batch based on low titanium dioxide content according to claim 7, wherein the twin-screw extruder adopts a screw combination mode, and the dispersion mixing is mainly adopted and the distribution mixing is auxiliary.
9. The preparation method of the shading master batch based on low titanium dioxide content according to claim 7 or 8, wherein the twin-screw extruder process for preparing the component A is as follows: the rotating speed of the screw is 310rpm, the yield is 150kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 235 ℃, temperature zone 3 is 235 ℃, temperature zone 4 is 235 ℃, temperature zone 5 is 235 ℃, temperature zone 6 is 235 ℃, temperature zone 7 is 235 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 225 ℃ and temperature zone 12 is 225 ℃.
10. The preparation method of the shading master batch based on low titanium dioxide content according to claim 7, wherein the conditions in the preparation process of the component B are as follows: mixing at high speed of 1500rpm for 5min, standing for 30-40min, and mixing at medium speed of 800rpm for 8 min.
11. The preparation method of the shading master batch based on low titanium dioxide content according to claim 7 or 8, wherein the process of the double-screw extruder for preparing the shading master batch is as follows: the rotating speed of the screw is 270rpm, the yield is 110kg/h, and the vacuum degree is less than or equal to-0.06 MPa; temperature zone 1 is 180 ℃, temperature zone 2 is 230 ℃, temperature zone 3 is 230 ℃, temperature zone 4 is 230 ℃, temperature zone 5 is 230 ℃, temperature zone 6 is 230 ℃, temperature zone 7 is 230 ℃, temperature zone 8 is 225 ℃, temperature zone 9 is 225 ℃, temperature zone 10 is 225 ℃, temperature zone 11 is 220 ℃ and temperature zone 12 is 220 ℃.
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