CN111925595A - Pearlescent master batch for biaxially oriented polypropylene film - Google Patents
Pearlescent master batch for biaxially oriented polypropylene film Download PDFInfo
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- CN111925595A CN111925595A CN202010831929.4A CN202010831929A CN111925595A CN 111925595 A CN111925595 A CN 111925595A CN 202010831929 A CN202010831929 A CN 202010831929A CN 111925595 A CN111925595 A CN 111925595A
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- 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
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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
- C08J2423/12—Polypropene
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- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- 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
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention discloses a pearlescent master batch for a biaxially oriented polypropylene film, which is prepared from the following raw materials in percentage by weight: 60-75% of heavy calcium carbonate, 2-3% of titanium dioxide, 1-5% of an activating agent, 1-5% of a processing aid, 5-10% of a flow modifier and 10-30% of PP resin; the processing aid is a fischer-tropsch wax and the flow modifier is an atactic polypropylene comb-block polyolefin comprised of a polyolefin backbone and at least two atactic polypropylene combs pendent from the polyolefin backbone and having a weight average molecular weight of at least 8000g/mol and a crystallinity of less than 20%. The invention adopts the coarse whiting and combines the specific processing aid and the flow modifier, thereby avoiding the coarse whiting from settling, having low production cost, effectively reducing the die head pressure and prolonging the filtering time. Tests prove that when the pearlescent master batch provided by the invention is used for production, the die head pressure is reduced by 30-40% compared with the prior art, the filtering time is prolonged to more than 25 days from the original less than 15 days, and the continuous production is realized without stopping the machine.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a pearlescent master batch for a biaxially oriented polypropylene film.
Background
The white and opaque BOPP pearlized film has the texture like silk, soft and beautiful pearl luster, low density, excellent smoothness and gas barrier property, and can be widely applied to the direct packaging of dry fruits, ice cream, candies, high-grade soap, gifts and the like.
Compared with the common BOPP film, the BOPP pearlized film has three typical characteristics: gives pearl luster, good light-shielding property and lower density. Particularly, the first two characteristics show different sound of the BOPP pearlized film, so that the BOPP pearlized film enters the high-end market in the field of packaging and brings considerable economic benefit for manufacturers. The BOPP pearlized film has the advantages that the excellent effect is achieved by the added pearlized master batch, countless uniform holes can be formed through stretching due to the fact that the adhesive force of calcium carbonate contained in the pearlized master batch to PP is low, and when light enters the holes, multi-level interference light generated due to light interference forms a pearlized effect; meanwhile, the addition of the calcium carbonate improves the light shading performance of the film, reduces the density of the film, and greatly reduces the production cost compared with the expensive and non-renewable polypropylene raw material. With the increase of the content of calcium carbonate in the BOPP pearlized film, the pearlized effect and the light-shading performance of the BOPP pearlized film become more excellent, and the cost is lower. Meanwhile, with the increase of the addition ratio of the pearlescent master batch, the dispersion difficulty of calcium carbonate in a polypropylene matrix is increased, the agglomeration is serious, and the problems of excessive reduction of the density of the BOPP film, reduction of the tensile strength and easy embrittlement are caused. Particularly, low-temperature embrittlement is more obvious, and the application of the BOPP pearlized film is restricted.
At present, each BOPP film manufacturer adopts a pearly-luster master batch containing a certain proportion of calcium carbonate to achieve a better dispersion effect in the production process. Because calcium carbonate and PP resin are incompatible, the difficulty of uniform dispersion of the calcium carbonate and PP resin in a BOPP film is high, calcium carbonate particles are easy to agglomerate to block a filter screen and break the film, the machine is often required to be stopped for cleaning, and the production efficiency and the yield are greatly reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the pearlescent master batch which has uniform and stable heavy calcium dispersion and effectively improves the low-temperature resistance of the BOPP film after the BOPP film is prepared.
In order to achieve the purpose, the invention adopts the following technical scheme.
The pearlescent master batch for the biaxially oriented polypropylene film is characterized by being prepared from the following raw materials in percentage by weight: 60-75% of heavy calcium carbonate, 2-3% of titanium dioxide, 1-5% of an activating agent, 1-5% of a processing aid, 5-10% of a flow modifier and 10-30% of PP resin; the processing aid is a fischer-tropsch wax and the flow modifier is an atactic polypropylene comb-block polyolefin comprised of a polyolefin backbone and at least two atactic polypropylene combs pendent from the polyolefin backbone and having a weight average molecular weight of at least 8000g/mol and a crystallinity of less than 20%.
More preferably, the pearlescent master batch for the biaxially oriented polypropylene film is prepared from the following raw materials in percentage by weight: 65-70% of heavy calcium carbonate, 2-3% of titanium dioxide, 2-3% of an activator, 2-4% of a processing aid, 5-8% of a flow modifier and 10-20% of PP resin.
More preferably, the pearlescent master batch for the biaxially oriented polypropylene film is prepared from the following raw materials in percentage by weight: 70% of heavy calcium carbonate, 3% of titanium dioxide, 3% of an activating agent, 2% of a processing aid, 5% of a flow modifier and 17% of PP resin.
More preferably, the activator is at least one of stearate, silane coupling agent, aluminum titanium composite coupling agent and titanate coupling agent.
More preferably, the preparation method of the atactic polypropylene comb-block polyolefin comprises the following steps: 1) contacting propylene with a first metallocene precursor and an activator at a temperature of 20-70 ℃ to form a vinyl terminated atactic polypropylene having a weight average molecular weight of at least 8000g/mol and a crystallinity of less than 20%; 2) contacting the vinyl terminated atactic polypropylene with ethylene, propylene, or both, a second metallocene precursor, and an activator at a temperature of 40 to 150 ℃ to form an atactic polypropylene comb-block polyolefin.
More preferably, the preparation method of the pearly-luster master batch of the biaxially oriented polypropylene film is as follows: 1) treating raw materials, namely uniformly stirring the coarse whiting, the titanium pigment, the activating agent, the processing aid and the flow improver in a high-speed stirrer, and adding PP resin for stirring when the surface temperature of the materials reaches 80-120 ℃ to uniformly mix the materials; 2) melt extrusion, adding the mixed materials into a double-screw extruder, extruding and filtering; 3) granulating and post-treating, cooling, air drying, granulating, drying and packaging the extruded materials to obtain finished products.
More preferably, in the step of processing the raw materials in the step 1), the stirring time of the coarse whiting, the titanium dioxide, the activating agent, the dispersing agent and the flow promoter is 20-30 minutes, and the stirring is carried out for 2-3 minutes after the PP resin is added.
More preferably, in step 2), the screw rotation speed of the twin-screw extruder is 400-500 rpm, and the extrusion temperature is between 190-240 ℃.
The invention has the beneficial effects that:
firstly, heavy calcium carbonate is adopted, and a specific processing aid and a flow modifier are combined, so that the heavy calcium carbonate is prevented from settling, the production cost is low, the die head pressure can be effectively reduced, the die head is not easy to block, and the filtering time is prolonged. Tests prove that when the pearlescent master batch provided by the invention is used for production, the die head pressure is reduced by 30-40% compared with the prior art, the filtering time is prolonged to more than 25 days from the original less than 15 days, and the continuous production is realized without stopping the machine.
Secondly, the BOPP film prepared by the pearlescent material has excellent tensile property and weather resistance, and particularly can keep tensile strength and softness basically unchanged at low temperature; effectively broadens the application field of BOPP.
Detailed Description
The following further describes the embodiments of the present invention, so that the technical solutions and the advantages thereof of the present invention are more clear and definite. The following description of the embodiments is exemplary in nature and is in no way intended to limit the invention.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Example 1
The pearly-luster master batch for the biaxially oriented polypropylene film is characterized by being prepared from the following raw materials in percentage by weight: 70% of heavy calcium carbonate, 3% of titanium dioxide, 1% of an activating agent, 2% of a processing aid, 5% of a flow promoter and 19% of PP resin.
Wherein the processing aid is Fischer-Tropsch wax, preferably EnHance type Fischer-Tropsch wax produced by Sasol of south Africa.
The compatibilized flow modifier is an atactic polypropylene comb-block polyolefin comprised of a polyolefin backbone and at least two atactic polypropylene combs pendant from the polyolefin backbone having a weight average molecular weight of at least 8000g/mol and a crystallinity of less than 20%; the processing aid is Fischer-Tropsch wax. The preparation method of the atactic polypropylene comb-block polyolefin comprises the following steps: 1) contacting propylene with a first metallocene precursor and an activator at a temperature of 20-70 ℃ to form a vinyl terminated atactic polypropylene having a weight average molecular weight of at least 8000g/mol and a crystallinity of less than 20%; 2) contacting the vinyl terminated atactic polypropylene with ethylene, propylene, or both, a second metallocene precursor, and an activator at a temperature of 40 to 150 ℃ to form an atactic polypropylene comb-block polyolefin.
The activating agent is a silane coupling agent. In other embodiments, the activator is at least one of a stearate, an aluminum titanium composite coupling agent, a titanate coupling agent; the present embodiment is not limited.
In practice, the procedure was as follows:
1) the raw materials are treated, the coarse whiting, the titanium pigment, the activating agent, the processing agent and the flow modifier are firstly stirred in a high-speed stirrer for 20-30 minutes, and then the PP resin is added and stirred for 2-3 minutes when the surface temperature of the materials reaches 80-120 ℃, so that the materials are uniformly mixed.
2) And (3) melt extrusion, namely adding the mixed materials into a double-screw extruder, wherein the rotating speed of the screw is 400-240 r/min, and the extrusion temperature is 190-240 ℃.
3) Granulating and post-treating, cooling, air drying, granulating, drying and packaging the extruded materials to obtain finished products.
The pearly-luster master batch for the biaxially oriented polypropylene film provided by the embodiment adopts the heavy calcium, and is combined with the specific processing aid and the flow modifier, so that the heavy calcium settlement is effectively reduced, the production cost is low, the die head pressure can be effectively reduced, and the filtering time is prolonged. Experiments prove that when the pearlescent master batch provided by the embodiment is used for production, the die head pressure is 40% lower than that of the prior art, the filtering time is prolonged to 30 days from the original less than 15 days, the machine does not need to be stopped, and the continuous production is realized.
Example 2
The pearlescent master batch for the biaxially oriented polypropylene film is characterized by being prepared from the following raw materials in percentage by weight: 75% of heavy calcium carbonate, 3% of titanium dioxide, 1% of an activating agent, 3% of a processing aid, 8% of a flow promoter and 10% of PP resin. Wherein the activating agent is an aluminum-titanium composite coupling agent,
the preparation method of the pearlescent master batch for the biaxially oriented polypropylene film provided by this embodiment is the same as that in embodiment 1, and details are not repeated here.
Tests prove that when the pearlescent master batch provided by the embodiment is used for production, the die head pressure is 38% lower than that of the prior art, the filtering time is prolonged to 28 days from the original less than 15 days, and the continuous production is realized without stopping the machine.
Example 3
The pearlescent master batch for the biaxially oriented polypropylene film is characterized by being prepared from the following raw materials in percentage by weight: 65% of heavy calcium carbonate, 2% of titanium dioxide, 5% of an activating agent, 5% of a processing aid, 5% of a flow promoter and 18% of PP resin. Wherein the activating agent is a mixture of stearate and a silane coupling agent.
The preparation method of the pearlescent master batch for the biaxially oriented polypropylene film with high filterability and high toughness provided in this example is the same as that in example 1, and is not described herein again.
Tests prove that by adopting the pearlescent master batch provided by the embodiment, during production, the die head pressure is reduced by 35% compared with the prior art, the filtering time is prolonged to 26 days from the original less than 15 days, and the continuous production is realized without stopping the machine.
Example 4
The pearly-luster master batch for the biaxially oriented polypropylene film is characterized by being prepared from the following raw materials in percentage by weight: 60% of heavy calcium carbonate, 2% of titanium dioxide, 1% of an activating agent, 1% of a processing aid, 6% of a flow promoter and 30% of PP resin. Wherein the activator is a titanate coupling agent.
The preparation method of the pearlescent master batch for the biaxially oriented polypropylene film with high filterability and high toughness provided in this example is the same as that in example 1, and is not described herein again.
Experiments prove that when the pearlescent master batch provided by the embodiment is used for production, the die head pressure is reduced by 30% compared with the prior art, the filtering time is prolonged to 25 days from the original less than 15 days, the machine does not need to be stopped, and the continuous production is realized.
Example 5
The pearly-luster master batch for the biaxially oriented polypropylene film is characterized by being prepared from the following raw materials in percentage by weight: 70% of heavy calcium carbonate, 2% of titanium dioxide, 1% of an activating agent, 1% of a processing aid, 10% of a flow promoter and 16% of PP resin. Wherein the activator is a titanate coupling agent.
The preparation method of the pearlescent master batch for the biaxially oriented polypropylene film with high filterability and high toughness provided in this example is the same as that in example 1, and is not described herein again.
Tests prove that when the pearlescent master batch provided by the embodiment is used for production, the die head pressure is reduced by 35% compared with the prior art, the filtering time is prolonged to 28 days from the original less than 15 days, and the continuous production is realized without stopping the machine.
Further, in order to better embody the technical progress of the present invention, the following steps were carried out to prepare a BOPP pearlescent film using the pearlescent master batch provided in examples 1 to 5, and the low temperature resistance of the BOPP pearlescent film was tested. The structure and the preparation process of the BOPP pearlescent film are the prior art, and comprise an upper surface layer, an intermediate layer and a lower surface layer, during experiments, the pearlescent master batch of the intermediate layer is replaced by the pearlescent master batch provided in the embodiments 1 to 5, and the others are kept unchanged. The results of the experiment are shown in tables 1 and 2.
TABLE 1 BOPP pearlized film Low temperature resistance test
TABLE 2 BOPP pearlized film Low temperature softness test
The experimental methods of table 2 are: taking a sample with the length of 250mm and the width of 100mm from a polypropylene film along the longitudinal direction of the film, uniformly spreading a layer of talcum powder on two surfaces of the sample and a stainless steel flat plate with the length of 400mm and the width of 200mm, flatly placing the sample on the stainless steel flat plate, folding the sample in half along the longitudinal direction, overlapping the head end and the tail end to form a flat ring shape, standing for 3min under the state, measuring the maximum height of two sides of the sample relative to the flat plate by using a graduated scale with the division value of 1mm, wherein the height represents the softness of the film, and the higher the height indicates that the softness of the film is worse.
As can be seen from tables 1 and 2, the BOPP pearlescent film prepared by the pearlescent master batch provided by the invention can keep the tensile strength and softness basically unchanged at low temperature; effectively broadens the application field of BOPP.
It will be understood by those skilled in the art from the foregoing description that the present invention is not limited to the specific embodiments described above, and that modifications and substitutions based on the known art are intended to be included within the scope of the present invention as defined by the appended claims and their equivalents. The details not described in the detailed description are prior art or common general knowledge.
Claims (8)
1. The pearlescent master batch for the biaxially oriented polypropylene film is characterized by being prepared from the following raw materials in percentage by weight: 60-75% of heavy calcium carbonate, 2-3% of titanium dioxide, 1-5% of an activating agent, 1-5% of a processing aid, 5-10% of a flow modifier and 10-30% of PP resin; the processing aid is a fischer-tropsch wax and the flow modifier is an atactic polypropylene comb-block polyolefin comprised of a polyolefin backbone and at least two atactic polypropylene combs pendent from the polyolefin backbone and having a weight average molecular weight of at least 8000g/mol and a crystallinity of less than 20%.
2. The pearlescent master batch for the biaxially oriented polypropylene film according to claim 1, which is characterized by being prepared from the following raw materials in percentage by weight: 65-70% of heavy calcium carbonate, 2-3% of titanium dioxide, 2-3% of an activator, 2-4% of a processing aid, 5-8% of a flow modifier and 10-20% of PP resin.
3. The pearlescent master batch for the biaxially oriented polypropylene film according to claim 1, which is characterized by being prepared from the following raw materials in percentage by weight: 70% of heavy calcium carbonate, 3% of titanium dioxide, 3% of an activating agent, 2% of a processing aid, 5% of a flow modifier and 17% of PP resin.
4. The pearlescent masterbatch for biaxially oriented polypropylene film according to claim 1, wherein the activator is at least one of stearate, silane coupling agent, aluminum titanium composite coupling agent and titanate coupling agent.
5. The pearlescent masterbatch for biaxially oriented polypropylene film according to claim 1, wherein the preparation method of the atactic polypropylene comb-block polyolefin comprises: 1) contacting propylene with a first metallocene precursor and an activator at a temperature of 20-70 ℃ to form a vinyl terminated atactic polypropylene having a weight average molecular weight of at least 8000g/mol and a crystallinity of less than 20%; 2) contacting the vinyl terminated atactic polypropylene with ethylene, propylene, or both, a second metallocene precursor, and an activator at a temperature of 40 to 150 ℃ to form an atactic polypropylene comb-block polyolefin.
6. The pearlescent master batch of the biaxially oriented polypropylene film according to claim 1, wherein the preparation method comprises the following steps:
1) treating raw materials, namely uniformly stirring the coarse whiting, the titanium pigment, the activating agent, the processing aid and the flow improver in a high-speed stirrer, and adding PP resin for stirring when the surface temperature of the materials reaches 80-120 ℃ to uniformly mix the materials;
2) melt extrusion, adding the mixed materials into a double-screw extruder, extruding and filtering;
3) granulating and post-treating, cooling, air drying, granulating, drying and packaging the extruded materials to obtain finished products.
7. The pearly-lustre master batch of the biaxially oriented polypropylene film according to claim 6, wherein in the step of processing the raw materials in the step 1), the heavy calcium carbonate, the titanium dioxide, the activating agent, the dispersing agent and the flow promoter are stirred for 20-30 minutes, and after the PP resin is added, the mixture is stirred for 2-3 minutes.
8. The pearlescent master batch of biaxially oriented polypropylene film according to claim 6, wherein in the step 2), the screw rotation speed of the twin-screw extruder is 400-500 rpm, and the extrusion temperature is 190-240 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113185774A (en) * | 2021-05-14 | 2021-07-30 | 广东帝通新材料股份有限公司 | High-filterability high-toughness biaxially oriented polypropylene film pearlescent master batch |
| CN115819891A (en) * | 2022-12-29 | 2023-03-21 | 苏州度辰新材料有限公司 | Polypropylene film master batch with high stiffness and preparation method thereof |
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Cited By (2)
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| CN113185774A (en) * | 2021-05-14 | 2021-07-30 | 广东帝通新材料股份有限公司 | High-filterability high-toughness biaxially oriented polypropylene film pearlescent master batch |
| CN115819891A (en) * | 2022-12-29 | 2023-03-21 | 苏州度辰新材料有限公司 | Polypropylene film master batch with high stiffness and preparation method thereof |
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