CN113321870A - Green color master batch for PPR pipe fittings and preparation method and application thereof - Google Patents
Green color master batch for PPR pipe fittings and preparation method and application thereof Download PDFInfo
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- CN113321870A CN113321870A CN202110662119.5A CN202110662119A CN113321870A CN 113321870 A CN113321870 A CN 113321870A CN 202110662119 A CN202110662119 A CN 202110662119A CN 113321870 A CN113321870 A CN 113321870A
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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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
- 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
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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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention provides a green color master for PPR pipe fittings and a preparation method and application thereof, wherein carrier resin is adopted as a matrix, and green powder and a dispersing agent with certain particle sizes are added to avoid agglomeration and reduce processing difficulty.
Description
Technical Field
The invention relates to the technical field of water supply plastic materials, in particular to a green color master batch for PPR (polypropylene random) pipe fittings and a preparation method and application thereof.
Background
The PPR pipe and pipe fittings are made by using sanitary-grade random polypropylene resin (PPR) as a main raw material, are excellent water supply plastic materials, have excellent physical and chemical properties, chemical corrosion resistance, high impact strength and small fluid resistance, have 30 percent of flow rate improvement compared with cast iron pipes with the same caliber, long service life and service life not less than 50 years, are ideal materials for cold and hot water supply of buildings, and usually add color master powder in the preparation process, but the compatibility of the color master powder and the PPR is poor, so that the performance of the PPR pipe and pipe fittings is reduced, and the application difficulty is brought; chinese patent CN109627611A discloses a high-dispersion low-precipitation color master batch for a PPR pipe based on polybutene and a preparation method thereof, wherein the compatibility of the color master batch and PPR is improved by utilizing the characteristic that the melt viscosity of the polybutene in a molten state is sharply reduced, and the dispersibility of the color master batch is further improved. However, polypropylene itself has compatibility problem with the system, so this method has little improvement on dispersibility, and in addition, the color master powder, especially the green powder, is generally made of pigment such as phthalocyanine green, and the whole volume is larger than that of other inorganic pigments, the particle size difference is large, the dispersion is more difficult, the dispersion of the green color master powder is uneven, so the stress concentration is caused, and the PPR product made from the green color master has poor weather resistance and is easy to separate out.
Disclosure of Invention
The invention aims to solve the technical problems that the existing green color master batch has poor dispersibility in PPR polymer resin, so that stress concentration is caused, and the prepared product has the defects of poor weather resistance and easy precipitation.
The invention further aims to provide a preparation method of the green color master batch for PPR pipe fittings.
The invention also aims to provide application of the green color master batch for PPR pipe fittings.
The above purpose of the invention is realized by the following technical scheme:
the green color master batch for the PPR pipe fitting comprises the following components in parts by weight:
70-80 parts of carrier resin;
40-50 parts of green powder;
5-25 parts of a dispersing agent;
1-2 parts of a slow release agent;
0.3-1.5 parts of an antioxidant;
0.2-1 part of a light stabilizer;
wherein the particle size of the green powder is 12000-13000 meshes; the particle size of the dispersing agent is 2000-3000 meshes.
The invention adopts carrier resin as a matrix, adjusts the component proportion, controls the mesh number of the green toner and the particle size of a dispersing agent, wherein the smaller the particle size of the toner is, the stronger the tinting strength is, but when the particle size of the toner reaches a certain critical range, the hiding power is reduced along with the reduction of the particle size, because when the particle size is smaller than half of the wavelength of light, the diffraction phenomenon of the light can occur, the transparency can be greatly increased, meanwhile, the particle size is too small, the larger the surface area is, the easier the agglomeration is to make the dispersion difficult, and the processing is difficult; the invention improves the compatibility of the green color master in the resin matrix by improving the components, improves the dispersibility of the green color master, further prepares products such as PPR pipe fittings and the like, is not easy to separate out, and can improve the weather resistance, low-temperature brittleness and mobility of the products.
Preferably, the composition comprises the following components in parts by weight:
70-75 parts of carrier resin;
35-45 parts of green powder;
10-15 parts of a dispersing agent;
1-1.5 parts of a slow release agent;
0.5-1.5 parts of an antioxidant;
0.2-0.5 part of light stabilizer.
Preferably, the particle size of the dispersing agent is 2500-3000 meshes.
Preferably, the particle size of the green powder is 12500-13000 meshes.
Preferably, the green powder is a phthalocyanine-based organic pigment.
Preferably, the carrier resin is a PPR resin.
Preferably, the dispersing agent is one or more of stearic acid, zinc stearate and polyethylene wax.
The slow release agent comprises one or more of montmorillonite and diatomite. The substances are all in a layered or hollow microporous structure, and can load light stabilizers and antioxidants into the substances, so that the aging of PPR green products can be effectively delayed.
The antioxidant of the present invention includes, but is not limited to, a complex of a hindered phenol antioxidant and a phosphite antioxidant. Can effectively prevent the degradation of resin and the yellowing of pigment in the processing process of the color master batch, thereby achieving the purpose of keeping the color stability of the color master batch.
The light stabilizer of the invention includes but is not limited to one of ultraviolet light absorbers and hindered amine light stabilizers. When the PPR pipeline is exposed outdoors, the high-energy ultraviolet light can cause the polymer to be broken, free radicals are generated, and the aging of the material is initiated, so that the substances can avoid the discoloration problem and the reduction of the mechanical property caused by the aging.
The invention discloses a preparation method of a green color master batch for protecting a PPR pipe fitting, which comprises the following steps:
mixing an antioxidant, a light stabilizer and a slow release agent in proportion, and grinding to obtain a mixed raw material; then respectively mixing the dispersing agent and the green powder, grinding and sieving; mixing the carrier resin, the green powder, the dispersing agent and the mixed raw materials, and banburying for 20-40 min at the banburying temperature of 160-210 ℃ to obtain a mixed material; and then melting and blending the mixture, extruding and granulating, and drying to obtain the green color master batch for the PPR pipe fitting.
Preferably, the banburying times are 1-3 times, and the single banburying time is 2-20 min. In order to improve the dispersion effect of the green powder in the high-density polyethylene resin, the dispersion effect can be realized by increasing the banburying times (repeating the banburying process) or the single banburying time, but the processing efficiency can be influenced, and the mechanical property of the masterbatch carrier random copolymerization polypropylene resin can be reduced due to too many times or too long single banburying time, so that the mechanical property of the pipe is influenced.
Preferably, the banburying adopts a continuous banbury mixer or a short-hand banbury mixer.
More preferably, the banburying is performed by a continuous banbury mixer.
Preferably, the melt blending adopts a screw extruder, the temperature of each zone is 190-220 ℃, and the rotating speed of the screw is 80-400 r/min.
The invention also protects the application of the green color master batch for preparing the water supply plastic material for the PPR pipe fitting.
Preferably, the method comprises the following steps:
and (2) uniformly mixing 100 parts by weight of PPR and 1.5-5 parts by weight of green color master, heating to 190-230 ℃, melting the mixed material into a fluid melt by heating, closing the die, injecting into a die, maintaining the pressure, cooling and forming to obtain the PPR pipe fitting.
Preferably, the green color master batch is 3 parts.
Preferably, the PPR and the green color master batch are added into a hopper and mixed uniformly.
A PPR water supply plastic material is prepared from the PPR pipe fitting by using green color masterbatch.
Compared with the prior art, the invention has the beneficial effects that:
the green color master batch for the PPR pipe fitting is used for preparing water supply plastic materials, and has the advantages of improving the compatibility of the color master batch powder and the resin matrix, improving the dispersibility of the color master batch powder, further using the green color master batch for preparing products such as the PPR pipe fitting and the like, preventing the products from being separated out easily, and improving the weather resistance, low-temperature brittleness and mobility of the products.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Examples 1 to 5 and comparative examples 1 to 4
The green color master batch for the PPR pipe fittings of the examples 1-5 and the comparative examples 1-4 comprises the components calculated according to the weight parts shown in the following table 1, and the difference between the examples 2-5 and the comparative examples 1-4 and the example 1 is the replacement of the components, and the preparation method is the same.
TABLE 1 Components and amounts (parts) of examples and comparative examples
The preparation method of the green color master batch for the PPR pipe fitting comprises the following steps:
firstly, mixing an antioxidant, a light stabilizer and a slow-release agent in proportion, placing the mixture in a grinding container, grinding the mixture for 10min by a high-speed grinder at the rotating speed of 500r/min, and uniformly grinding the mixture to obtain a mixed raw material; respectively adding the dispersing agent and the green powder into a sanding disperser, grinding at the rotating speed of 2000 r/min, sieving the dispersing agent grinding particles, and sieving the green powder grinding particles;
premixing the carrier resin, the treated dispersant, the green powder and the mixed raw materials at room temperature for 3 minutes at a low speed in a 100-rpm mixer, then mixing the mixture at a high speed for 6 minutes at 800 rpm in a high-speed mixer, adding the mixture into an internal mixer, and mixing for 3 times, 15 minutes each time, wherein the internal mixing temperature is 200 ℃ to obtain a mixture; then a double-screw extruder is adopted for melt blending granulation, the temperature of 5 temperature zones in the extruder is set to be 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃, the rotating speed of a main engine is 500r/min, and the extrudate is cooled at 20 ℃; and granulating the hardened substance by using a granulator, sieving the hardened substance by using a fine vibrating screen to remove irregular products, ventilating, and completely cooling and drying the color master batch to obtain a finished product.
Applications of
Preparing a PPR pipe fitting:
s1, uniformly mixing 100 parts of PPR (polypropylene random copolymer) by weight and 3 parts of green color masterbatch prepared in each embodiment or comparative example, and adding the mixture into a hopper;
s2, heating the glue melting cylinder of the injection device in the step S1 to enable the temperature in the glue melting cylinder of the injection device to reach 190-230 ℃, and heating and melting the mixed material to form a fluid melt;
s3, after the die assembly is completed, injecting the fluid melt into a forming cavity of a forming die through an injection device;
and S4, after the injection filling in the step S3 is finished, pressure maintaining and cooling are carried out, and after the cooling is finished, the mold is opened to obtain the PPR pipe fitting.
Performance testing
1. In order to scientifically and reasonably obtain the proportion of the green color master batch with better processability, the green color master batch is compared through rheological experiments, wherein the rheological experiments specifically comprise the following steps:
(1) weighing 100 parts of PPR raw material and 3 parts of color master batch;
(2) turning on a torque rheometer, setting the temperature at 200 ℃, the rotor speed at 40r/min and the time at 15 min;
(3) adding weighed materials after the instrument stably operates;
(4) recording the rheological curve of each sample and finishing the data; the results are shown in table 2 below:
TABLE 2 processability of Green concentrates obtained in examples and comparative examples
As can be seen from the data in table 2, as the amount of the dispersant increases, the plasticizing torque and the equilibrium torque decrease accordingly, the torque becomes too high, and the processing becomes difficult, but the torque becomes too low, and the pipe is not easily molded when processed, and the amount of the dispersant added increases, and the cost also increases. For this reason, it is most reasonable to use 15 parts of the dispersant under the condition that the plasticizing torque and the balance torque can be stably processed.
When the consumption of the green powder is basically unchanged, the amount of the dispersing agent added is more reasonable, scientific and economical when the consumption is 10-15 parts, and 15 parts are taken according to the actual processing condition to achieve the best effect, and the dispersing agent is required to be sieved. In addition, as can be seen from table 2, the mesh number of the green color powder reaches 12500 meshes, and the processability of the green color master batch is the best. 2. The appearance, color difference, density, moisture content, water migration, melt index, ash content and melting temperature performance of the green master batch are detected, and the results are as follows:
table 3 Performance test results of the green color concentrates prepared in examples 1 to 7
The test results in table 3 show that the green color masterbatch prepared in examples 1 to 5 has excellent performance.
3. The green master batch prepared in the embodiment 3 is taken according to 3 parts and 100 parts of PPR to prepare PPR green pipes and pipe fittings, then the pigment dispersibility is checked, the conventional pipes and pipe fittings prepared by the master batch in the comparative example 1 are also checked for comparison, and the dispersion degree test method comprises the following steps: the samples of the films hot-pressed from the mixes were examined by means of an optical microscope under transmitted light, and the degree of microdispersion of the product was rated according to the size and number of aggregates which were dispersed. The apparent grade of dispersion is described as being measured under a magnification of "× 70", the smaller the grade, the better the dispersion. Wherein the new formula is as follows: example 3 pipe fitting made of green masterbatch, old formulation is the pipe fitting made of green masterbatch of comparative example 1.
TABLE 4 pigment Dispersion grades for tubing and pipe fittings made with different formulations
As can be seen from the above test data, the dispersibility of the present invention is 2.2 or less. Compared with the prepared PPR pipe and pipe fitting of the comparative example 1, the PPR pipe and pipe fitting are more excellent, and the green powder of the comparative example 1 has too small particle size, is easy to agglomerate, makes the dispersion difficult and is difficult to process. The green powder of comparative example 2 had too large a particle diameter and small a specific surface area, and thus had poor hiding power and low coloring power. The particle size of the dispersant used in comparative examples 3 and 4 is too small or too large, and the dispersibility cannot be improved well.
The appearance of weather resistance and low-temperature brittleness resistance refers to pipe cracking, and the cracking is generally caused by cracking at a certain point due to stress concentration, then rapidly expanding and finally forming brittle cracking. The PPR green color master batch prepared by the invention adjusts the component proportion and controls the mesh number of the green powder and the particle size of the dispersant, and the improved PPR green color master batch can be uniformly dispersed in a resin matrix without causing stress concentration, so that the PPR pipe and pipe fittings prepared by further utilizing the PPR green color master batch are not easy to separate out, and the weather resistance, low-temperature brittleness and mobility of products can be improved.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The green color master batch for the PPR pipe fittings is characterized by comprising the following components in parts by weight:
70-80 parts of carrier resin;
40-50 parts of green powder;
5-25 parts of a dispersing agent;
1-2 parts of a slow release agent;
0.3-1.5 parts of an antioxidant;
0.2-1 part of a light stabilizer;
wherein the particle size of the green powder is 12000-13000 meshes; the particle size of the dispersing agent is 2000-3000 meshes.
2. The green color master batch for the PPR pipe fittings according to claim 1, which is characterized by comprising the following components in parts by weight:
70-75 parts of carrier resin;
35-45 parts of green powder;
10-15 parts of a dispersing agent;
1-1.5 parts of a slow release agent;
0.5-1.5 parts of an antioxidant;
0.2-0.5 part of light stabilizer.
3. The green color master batch for the PPR pipe fittings according to claim 1 or 2, wherein the particle size of the dispersing agent is 2500-3000 meshes.
4. The green color master batch for the PPR pipe fitting as claimed in claim 1, wherein the particle size of the green color master batch is 12500-13000 meshes.
5. The green color masterbatch for PPR pipe fittings according to claim 1, wherein the carrier resin is PPR resin.
6. The green color master batch for the PPR pipe fittings according to claim 1, wherein the dispersing agent is one or more of stearic acid, zinc stearate and polyethylene wax.
7. The preparation method of the green color master batch for the PPR pipe fittings, which is disclosed by any one of claims 1-6, is characterized by comprising the following steps:
mixing an antioxidant, a light stabilizer and a slow release agent in proportion, and grinding to obtain a mixed raw material; then respectively mixing the dispersing agent and the green powder, grinding and sieving; mixing the carrier resin, the green powder, the dispersing agent and the mixed raw materials, and banburying for 20-40 min at the banburying temperature of 160-210 ℃ to obtain a mixed material; and then melting and blending the mixture, extruding and granulating, and drying to obtain the green color master batch for the PPR pipe fitting.
8. The preparation method according to claim 7, wherein the banburying times are 1-3 times, and the single banburying time is 2-20 min.
9. The use of the green color master batch for the PPR pipe fittings of any one of claims 1-6 in the preparation of water-supply plastic materials.
10. The PPR water supply plastic material is characterized by comprising the PPR pipe fitting as claimed in any one of claims 1-6, and the PPR pipe fitting is prepared from green color master batch.
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| CN202110662119.5A CN113321870A (en) | 2021-06-15 | 2021-06-15 | Green color master batch for PPR pipe fittings and preparation method and application thereof |
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| CN202110662119.5A CN113321870A (en) | 2021-06-15 | 2021-06-15 | Green color master batch for PPR pipe fittings and preparation method and application thereof |
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2021
- 2021-06-15 CN CN202110662119.5A patent/CN113321870A/en active Pending
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| CN104497424A (en) * | 2014-12-05 | 2015-04-08 | 成都菲斯特化工有限公司 | Coloring masterbatch for PPR tube and preparation method of coloring masterbatch |
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