CN114106485A - Polyvinyl chloride material and preparation method and application thereof - Google Patents
Polyvinyl chloride material and preparation method and application thereof Download PDFInfo
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- CN114106485A CN114106485A CN202111370420.5A CN202111370420A CN114106485A CN 114106485 A CN114106485 A CN 114106485A CN 202111370420 A CN202111370420 A CN 202111370420A CN 114106485 A CN114106485 A CN 114106485A
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- polyvinyl chloride
- chloride material
- polyethylene wax
- pipe
- acid ester
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
Abstract
The invention belongs to the technical field of plastic pipelines, and particularly relates to a polyvinyl chloride material as well as a preparation method and application thereof. According to the invention, a certain amount of montanic acid ester and oxidized polyethylene wax are added in the formula, and the cooperation of the montanic acid ester and the oxidized polyethylene wax ensures that the hard polyvinyl chloride pipe prepared from the polyvinyl chloride material has good demoulding effect and high appearance glossiness, the mould does not have scaling phenomenon in a production period of 60 days, the mould cleaning time is effectively saved, and the production efficiency is improved; in addition, the pipe of the application also has excellent tensile yield strength and impact resistance.
Description
Technical Field
The invention belongs to the technical field of plastic pipelines. More particularly, relates to a polyvinyl chloride material, a preparation method and an application thereof.
Background
Polyvinyl chloride (PVC) is a general-purpose plastic prepared by free radical polymerization of Vinyl Chloride Monomer (VCM), and can be used for preparing hard polyvinyl chloride (PVC-U) products and soft polyvinyl chloride (PVC-U) products meeting different purposes by adding proper auxiliaries. The hard polyvinyl chloride product mainly comprises a pipe material, a pipe fitting, a door and window section bar, a plate material, a sheet material, an electric wire insulating skin, a medical article, a film, a sealing strip and the like.
The hard polyvinyl chloride (PVC-U) pipe has the advantages of long service life, smooth inner and outer walls, corrosion resistance and the like which are not compared with a cast iron pipe and a cement pipe; the construction method has the characteristics of high carrying efficiency, convenient and reliable connection and the like, and is widely applied to the fields of drainage and pollution discharge of buildings, discharge of corrosive sewage and rainwater in chemical plants and the like.
The formula of the hard polyvinyl chloride (PVC-U) pipe at the present stage mainly comprises polyvinyl chloride resin, calcium carbonate, a calcium-zinc stabilizer, an impact resistant agent, a processing aid, a lubricant, titanium dioxide and the like, wherein the lubricant directly influences the processing efficiency of the pipe and the performance of the final pipe, so the selection of the lubricant is particularly important. In a calcium-zinc stabilizer system, a lubricant generally adopts polyethylene wax with a strong external lubricating effect, although the polyethylene wax can efficiently adjust the plasticizing effect of a formula to adapt to extrusion processing molding of pipes, the polyethylene wax is a non-polar polymer and is completely immiscible with polar polyvinyl chloride, so that the demolding effect on polyvinyl chloride melts is poor, and the pipes are easy to scale, thereby causing the problem of poor appearance glossiness. For example, the prior art discloses a production formula for improving the glossiness of the outer wall of the pipe, which has the effect of improving the glossiness of the inner wall and the outer wall of the pipe to a certain extent, but the external lubricant is polyethylene wax, which has poor demolding effect on polyvinyl chloride melt, and the pipe is easy to scale and has appearance glossiness to be improved.
Disclosure of Invention
The invention aims to solve the technical problems that the prior hard polyvinyl chloride (PVC-U) has poor demoulding effect, so that the pipe is easy to scale and the appearance gloss is still to be improved, and provides a polyvinyl chloride material capable of preparing the pipe with good demoulding effect, difficult scaling and excellent gloss.
The invention aims to provide a preparation method of a polyvinyl chloride material.
Another object of the present invention is to provide a rigid polyvinyl chloride pipe.
The invention also aims to provide a preparation method of the rigid polyvinyl chloride pipe.
The above purpose of the invention is realized by the following technical scheme:
a polyvinyl chloride material comprises the following components in parts by weight:
the polyvinyl chloride resin powder is one or more of SG-5, K66 or S1000.
Preferably, the weight part ratio of the montanic acid ester to the oxidized polyethylene wax is (1-5): 1.
Preferably, the dropping point of the montanic acid ester is 100-104 ℃, and the acid value is 13-18 mgKOH/g.
More preferably, the montanic acid ester has a drop point of 102 ℃ and an acid value of 15 mgKOH/g.
Preferably, the melting point of the oxidized polyethylene wax is 103-105 ℃, and the acid value is 27-29 mgKOH/g.
More preferably, the oxidized polyethylene wax has a melting point of 103 ℃ and an acid value of 28 mgKOH/g.
Preferably, the internal lubricant is one or more of fatty acid ester, fatty acid metal soap, fatty acid amide.
More preferably, the fatty acid ester is a monoglyceride or dioctadecyl phthalate (G60); the fatty acid metal soap is calcium stearate or zinc stearate.
Preferably, the external lubricant is one or more of polyethylene wax and paraffin wax.
More preferably, when the internal lubricant is monoglyceride, the external lubricant is polyethylene wax; or when the internal lubricant is dioctadecyl phthalate, the external lubricant is paraffin.
Because the calcium-zinc stabilizer contains strongly polar calcium stearate and calcium acetylacetonate, after the rigid polyvinyl chloride pipe formula system adopting the calcium-zinc stabilizer is extruded and produced for a long time, the calcium stearate and the calcium acetylacetonate in a melt are adhered to the surface of a polar metal mould, and a layer of substance similar to scale is formed on the surface of the mould after long-term accumulation, and the main components of the scale are polyvinyl chloride, calcium carbonate and titanium dioxide, and the phenomenon is commonly called as scaling in the industry. The addition of a certain amount of montanic acid ester and oxidized polyethylene wax in the formula can avoid the phenomenon of scaling, and the glossiness of the inner wall and the outer wall of the pipe is improved. The montanic acid ester is composed of a strong polar main body and a nonpolar long-chain alkyl group, the strong polar main body is dissolved with polar polyvinyl chloride to play an internal lubrication role, and the nonpolar long-chain alkyl group is not dissolved with the polyvinyl chloride to play an external lubrication role. But the montanic acid ester has a low acid value, poor complexing ability with polyvinyl chloride and easy dissociation, and the oxidized polyethylene wax has a higher acid value than the montanic acid ester, more polar groups on a molecular chain, better compatibility with the polyvinyl chloride and higher complexing ability, and can effectively solve the problem that the montanic acid ester is easy to dissociate. Meanwhile, the oxidized polyethylene wax has larger molecular weight, can form a firm lubricating film with the metal surface of processing equipment at high temperature, has obvious demolding effect, and can be used together with montanic acid ester with lower acid value to further improve the demolding effect.
Preferably, the auxiliary agent comprises heavy calcium carbonate, an impact modifier, a processing modifier and titanium dioxide.
Specifically, the auxiliary agent comprises the following components in parts by weight:
the content of calcium carbonate in the heavy calcium carbonate is more than or equal to 95 percent, the particle size is less than or equal to 5.5 mu m, and the whiteness is more than or equal to 92 percent.
The invention also provides a preparation method of the polyvinyl chloride material, which comprises the following steps:
stirring and mixing the components according to a certain amount, heating to 112-118 ℃, and cooling to obtain the product.
The invention also discloses a hard polyethylene pipe prepared from the polyvinyl chloride material.
The invention also discloses a preparation method of the hard polyethylene pipe, which comprises the following steps:
s1, stirring and mixing all the components according to a certain amount, heating to 112-118 ℃, and cooling to obtain a primary product;
and S2, performing molding forming on the primary product obtained in the step S1 at 165-205 ℃, cooling, measuring length and cutting to obtain the product.
Preferably, in step S1, the cooling process is performed by stirring until the temperature of the cold mixing tank drops below 50 ℃.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a certain amount of montanic acid ester and oxidized polyethylene wax are added in the formula, and through the synergistic effect of the montanic acid ester and the oxidized polyethylene wax, the hard polyvinyl chloride pipe prepared from the polyvinyl chloride material has good demolding effect and high appearance glossiness, the mold does not have a scaling phenomenon in a production period of 60 days, the mold cleaning time is effectively saved, and the production efficiency is improved; in addition, the pipe of the application also has excellent tensile yield strength and impact resistance.
Drawings
FIG. 1 is a graph showing the absence of "fouling" of the tubing mold obtained in example 3.
FIG. 2 is a graph showing the "fouling" of the pipe mold obtained in comparative example 1.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The model of the polyvinyl chloride resin powder is SG-5, Xinjiang Zhongtai chemical Co., Ltd;
montanic acid ester has a dropping point of 102 ℃ and an acid value of 15mgKOH/g, and is prepared by the Kelain chemical industry;
montanic acid ester has a dropping point of 80 ℃, an acid value of 23mgKOH/g, and is prepared by the Kelain chemical industry;
the melting point of the oxidized polyethylene wax is 103 ℃, the acid value is 28mgKOH/g, and Nanjing Tianshi New Material Co., Ltd;
the melting point of the oxidized polyethylene wax is 95 ℃, the acid value is 16mgKOH/g, and Nanjing Tianshi New Material Co., Ltd;
the calcium zinc stabilizer is R91595R/5, Halroche plastics additives (Jiangsu) Co.
EXAMPLES 1 to 7 preparation of polyvinyl chloride Material
A polyvinyl chloride material is prepared by stirring and mixing the following components according to certain dosage, heating to 112-118 ℃ and cooling, wherein the components and the dosages are shown in Table 1:
table 1: examples 1 to 7 formulations of polyvinyl chloride Material
Comparative examples 1 to 4 preparation of polyvinyl chloride Material
A polyvinyl chloride material is prepared by stirring and mixing the following components according to certain dosage, heating to 112-118 ℃ and cooling, wherein the components and the dosages are shown in Table 2:
table 2: formula of polyvinyl chloride material in comparative examples 1-4
And (3) testing:
1. preparation of rigid polyvinyl chloride pipe
1.1 the preparation method comprises the following steps:
the polyvinyl chloride material obtained in the embodiments 1-7 and the material obtained in the comparative examples 1-4 are prepared into a pipe, and the method comprises the following steps:
s1, adding the components into a hot mixing cylinder of a high-speed mixer set according to a certain amount (the raw materials and the amount of the raw materials are shown in tables 1 and 2), discharging the mixture into a cold mixing cylinder after high-speed stirring until the temperature of the hot mixing cylinder reaches 115 ℃, stirring and cooling the mixture, and stopping stirring when the temperature of the cold mixing cylinder is reduced to below 50 ℃ to obtain a primary product;
s2, adding the primary product obtained in the step S1 into a parallel counter-rotating double-screw extruder for plasticizing, molding and forming, cooling, measuring length and cutting to obtain the product, wherein the temperature of a machine barrel of the parallel counter-rotating double-screw extruder is 183-169 ℃, and the molding temperature is 165-203 ℃.
The outer diameter of the obtained pipe is 110mm, and the wall thickness is 3.2 mm.
2. Performance testing
The rigid polyvinyl chloride (PVC-U) pipes prepared in the above examples and comparative examples are tested according to the standard requirements of GB/T5836.1-2006 rigid polyvinyl chloride (PVC-U) pipes for building drainage, and the specific test results are shown in tables 3-6.
2.1 testing the tensile yield strength, drop hammer impact and longitudinal retraction rate. The test results are shown in tables 3 and 4.
Table 3: performance results of rigid polyvinyl chloride (PVC-U) pipes prepared from the polyvinyl chloride materials described in examples 1-7
Table 4: performance results of rigid polyvinyl chloride (PVC-U) pipes prepared from the polyvinyl chloride materials described in comparative examples 1-4
| Detecting items | Standard for | Comparative example 1 | Comparative example 2 | Comparative example | Comparative example |
| Tensile yield strength | ≧40MPa | 42.5MPa | 41.8MPa | 40.7MP | 40.5MP |
| Impact of drop hammer | TIR≦10 | TIR＝5％ | TIR＝5％ | TIR＝5 | TIR＝5 |
| Longitudinal shrinkage | ≦5％ | 4.5％ | 4.1％ | 4.3％ | 4.6％ |
Shown by the data in tables 3 and 4: the tensile yield strength, drop weight impact and longitudinal retraction rate of the rigid polyvinyl chloride (PVC-U) pipes prepared from the polyvinyl chloride materials in examples 1-7 and comparative examples 1-4 all meet the standard requirements, and the polyvinyl chloride materials can be used for preparing the rigid polyvinyl chloride (PVC-U) pipes meeting the standards.
2.2 testing the scaling condition of the die and the glossiness of the outer wall. The test results are shown in tables 5 and 6.
Table 5: example 1-7 pipes prepared from the polyvinyl chloride materials described in examples 1 were subjected to mold fouling and pipe outer wall gloss for 60 days after continuous production
The gloss was measured according to ASTM D2457-2003 Standard test method for specular gloss of Plastic films and solid plastics.
Table 6: comparative examples 1-4 pipes prepared from the polyvinyl chloride material are subjected to mold scaling and pipe outer wall glossiness after continuous production for 60 days
According to the data analysis of the embodiments and the comparative examples, the pipes prepared in the embodiments have the advantages of good demoulding effect and high glossiness. As shown in fig. 1: the pipe prepared from the polyvinyl chloride material in the embodiment 3 has a smooth surface and no scaling phenomenon; in comparative example 1, the mould surface prepared without adding montanic acid ester or oxidized polyethylene wax has more than 30% of scale (as shown in figure 2), and the glossiness of the outer wall is obviously lower than that of the PVC-U pipe prepared in the example, which proves that the glossiness of the outer wall of the pipe can be effectively improved by adding montanic acid ester and oxidized polyethylene wax.
As can be seen from tables 1 to 6, the tensile yield strength, drop weight impact, longitudinal shrinkage, mold scaling condition and outer wall gloss of the rigid polyvinyl chloride (PVC-U) pipe prepared from the polyvinyl chloride materials described in examples 1 to 7 all meet the standard requirements.
Example 4 differs from example 2 only in that the oxidized polyethylene wax (melting point 103 ℃, acid value 28mgKOH/g) in example 2 is replaced by oxidized polyethylene wax (melting point 95 ℃, acid value 16mgKOH/g), the outer wall gloss is reduced by 2%, thus, the addition of oxidized polyethylene wax can effectively increase the gloss of the polyethylene pipe, but the oxidized polyethylene wax with melting point 103 ℃ and acid value 28mgKOH/g has better effect.
Example 5 differs from example 1 only in that the external wall gloss was reduced by 2% by replacing the montanic acid ester (dropping point 102 ℃ C., acid value 15mgKOH/g) of example 1 with montanic acid ester (dropping point 80 ℃ C., acid value 23mgKOH/g), and it can be seen that the addition of montanic acid ester can effectively increase the gloss of polyethylene pipe, but montanic acid ester having dropping point 102 ℃ C., acid value 15mgKOH/g is more effective.
Example 6 differs from example 3 only in that the gloss of the outer wall of the polyethylene pipe is reduced by 3% by replacing the inner lubricant of example 3 with the monoglyceride of example 3, and it can be seen that the addition of the inner and outer lubricants is effective in increasing the gloss of the polyethylene pipe, but the effect is better when the inner lubricant is monoglyceride and the outer lubricant is polyethylene wax than when the inner lubricant is stearic acid and the outer lubricant is polyethylene wax.
Example 7 differs from example 3 only in that the external lubricant in example 3 was replaced with the polyethylene wax in example 3 to microcrystalline wax, and the gloss of the outer wall was reduced by 2%, and it can be seen that the addition of the internal lubricant and the external lubricant was effective in increasing the gloss of the polyethylene pipe, but the effect of the internal lubricant being monoglyceride and the external lubricant being polyethylene wax was better than the effect of the internal lubricant being monoglyceride and the external lubricant being microcrystalline wax.
As can be seen from the above, in the preparation process of the rigid polyvinyl chloride (PVC-U) pipe prepared by adding a certain amount of montanic acid ester and oxidized polyethylene wax in the embodiments of the invention, the rigid polyvinyl chloride (PVC-U) pipe prepared by the synergistic effect of montanic acid ester and oxidized polyethylene wax and the appropriate adjustment of the dosage of other components completely meets the standard requirements of GB/T5836.1-2006 rigid polyvinyl chloride (PVC-U) pipe for building drainage. The pipe has excellent tensile yield strength and impact resistance; in addition, the mold has no scaling phenomenon in the production period of 60 days, the glossiness of the outer wall of the pipe is obviously improved, the time for cleaning the mold is saved, and the production efficiency is improved. The problem that after the rigid polyvinyl chloride pipe formula system adopting the calcium-zinc stabilizer is extruded continuously for a long time, calcium stearate and calcium acetylacetonate in a melt are adhered to the surface of a polar metal mould, and a layer of substances similar to scale is formed on the surface of the mould after the rigid polyvinyl chloride pipe formula system is extruded for a long time can be effectively solved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The polyvinyl chloride material is characterized by comprising the following components in parts by weight:
2. the polyvinyl chloride material according to claim 1, wherein the weight ratio of the montanic acid ester to the oxidized polyethylene wax is (1-5): 1.
3. The polyvinyl chloride material of claim 1, wherein the internal lubricant is one or more of a fatty acid ester, a fatty acid metal soap, a fatty acid amide.
4. The polyvinyl chloride material of claim 3, wherein the fatty acid ester is a monoglyceride or a dioctadecyl phthalate; the fatty acid metal soap is calcium stearate or zinc stearate.
5. The polyvinyl chloride material according to claim 1, wherein the external lubricant is one or more of polyethylene wax and paraffin wax.
6. The polyvinyl chloride material according to claim 1, wherein when the internal lubricant is monoglyceride, the external lubricant is polyethylene wax; or when the internal lubricant is dioctadecyl phthalate, the external lubricant is paraffin.
7. The polyvinyl chloride material of claim 1, wherein the additives comprise ground calcium carbonate, impact modifier, processing modifier, titanium dioxide.
8. A method for preparing a polyvinyl chloride material according to any one of claims 1 to 7, comprising the steps of:
stirring and mixing the components according to the dosage, heating to 112-118 ℃, and cooling to obtain the product.
9. A rigid polyvinyl chloride pipe material, which is characterized by being prepared from the polyvinyl chloride material as claimed in any one of claims 1 to 7.
10. A method of making a rigid polyvinyl chloride pipe material according to claim 9, comprising the steps of:
s1, stirring and mixing the components according to the using amount, heating to 112-118 ℃, and cooling to obtain a primary product;
and S2, performing molding forming on the primary product obtained in the step S1 at 165-205 ℃, cooling, measuring length and cutting to obtain the product.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2018720A1 (en) * | 1970-04-18 | 1971-11-04 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Hard wax from montan wax and polyethy-lene and/or oxidised polyethyle - wax |
| US4129536A (en) * | 1977-07-25 | 1978-12-12 | Rca Corporation | Vinyl chloride based injection molding composition |
| US4518732A (en) * | 1978-05-19 | 1985-05-21 | Ciba Geigy Corporation | Solid stabilizer composition |
| JP2010185043A (en) * | 2009-02-13 | 2010-08-26 | Kyodo Yushi Co Ltd | Grease composition for resin lubrication |
| CN102911460A (en) * | 2012-10-25 | 2013-02-06 | 山东群升伟业塑胶科技有限公司 | High weather-resistant low-smoke halogen-free flame-retardant rigid polyvinyl chloride pipe and preparation process thereof |
-
2021
- 2021-11-18 CN CN202111370420.5A patent/CN114106485A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2018720A1 (en) * | 1970-04-18 | 1971-11-04 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Hard wax from montan wax and polyethy-lene and/or oxidised polyethyle - wax |
| US4129536A (en) * | 1977-07-25 | 1978-12-12 | Rca Corporation | Vinyl chloride based injection molding composition |
| US4518732A (en) * | 1978-05-19 | 1985-05-21 | Ciba Geigy Corporation | Solid stabilizer composition |
| JP2010185043A (en) * | 2009-02-13 | 2010-08-26 | Kyodo Yushi Co Ltd | Grease composition for resin lubrication |
| CN102911460A (en) * | 2012-10-25 | 2013-02-06 | 山东群升伟业塑胶科技有限公司 | High weather-resistant low-smoke halogen-free flame-retardant rigid polyvinyl chloride pipe and preparation process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周祥兴: "《中国塑料制品配方大全》", 31 May 1999 * |
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