CN111234376A - Scratch-resistant flame-retardant PP material, preparation method thereof and toilet seat - Google Patents
Scratch-resistant flame-retardant PP material, preparation method thereof and toilet seat Download PDFInfo
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- CN111234376A CN111234376A CN202010057316.XA CN202010057316A CN111234376A CN 111234376 A CN111234376 A CN 111234376A CN 202010057316 A CN202010057316 A CN 202010057316A CN 111234376 A CN111234376 A CN 111234376A
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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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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
- A47K13/00—Seats or covers for all kinds of closets
- A47K13/02—Seats or covers for all kinds of closets of plastic materials
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses a scratch-resistant flame-retardant PP material, a preparation method thereof and a toilet seat ring, wherein the scratch-resistant flame-retardant PP material comprises the following raw materials in parts by weight: 70-80 parts of homopolymerized polypropylene resin, 10-20 parts of precipitated barium sulfate, 3-4 parts of flame retardant, 0.2-0.3 part of nucleating agent, 1-2 parts of lubricating dispersant, 0.2-0.5 part of antioxidant, 0.1-0.3 part of oleamide, 0.1-0.3 part of erucamide and 0.5-2 parts of scratch-resistant agent. The scratch-resistant flame-retardant PP material can be used for preparing toilet seats, has good flame retardance and scratch resistance, and can still maintain excellent scratch resistance after being washed by a detergent.
Description
Technical Field
The invention relates to the technical field of PP (polypropylene) material preparation, in particular to a scratch-resistant flame-retardant PP material, a preparation method thereof and a toilet seat.
Background
At present, the material of the intelligent toilet seat is generally made of flame-retardant PP (polypropylene) material or flame-retardant ABS (acrylonitrile-butadiene-styrene copolymer) material. The flame-retardant ABS material has good scratch resistance, but has high cost and is heavier; the flame-retardant PP material is low in price and light in weight, but the scratch resistance of the conventional PP material is poor. Further, most toilet seats on the market at present are not scratch-resistant, are easily scratched by hard objects such as fingernails and washing brushes of people in the processes of production, use and cleaning, and are easy to generate static electricity to adsorb dust, hair and the like.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a scratch-resistant flame-retardant PP material, a preparation method thereof and a toilet seat ring.
The technical scheme adopted by the invention is as follows:
the invention provides a scratch-resistant flame-retardant PP material, which comprises the following raw materials in parts by weight: 70-80 parts of homopolymerized polypropylene resin, 10-20 parts of precipitated barium sulfate, 3-4 parts of flame retardant, 0.2-0.3 part of nucleating agent, 1-2 parts of lubricating dispersant, 0.2-0.5 part of antioxidant, 0.1-0.3 part of oleamide, 0.1-0.3 part of erucamide and 0.5-2 parts of scratch-resistant agent.
According to some embodiments of the invention, the flame retardant is a bromine phosphorus nitrogen based flame retardant; the bromine phosphorus nitrogen flame retardant contains 30-35% of phosphorus, 30-35% of nitrogen and 8-12% of bromine. The flame retardant is adopted, the addition amount is small, and the bromine content of the product is extremely low on the basis of ensuring the flame retardant performance of the PP material, and is greatly lower than the halogen-free requirement of European Union; the combustion substances are environment-friendly, and the problem of dioxin is avoided; the flame retardant is high temperature resistant, does not precipitate and has no adverse effect on the surface glossiness of the product.
According to some embodiments of the invention, the scratch-resistant agent is a reactive high polysiloxane, specifically a reactive high polysiloxane produced by Ciba refinement, Inc., and the reactive high polysiloxane contains a special functional group, so that the reactive high polysiloxane can play an anchoring role in PP resin, has good compatibility with PP materials, is migration resistant, and can still have excellent scratch resistance after being washed by a detergent.
According to some embodiments of the present invention, the homopolypropylene resin has a melt index of 20 to 30g/10min at 230 ℃ under a 2.16kg test condition. The adoption of the homo-polypropylene resin is beneficial to improving the glossiness of the product.
According to some embodiments of the invention, the nucleating agent is a sorbitol-based nucleating agent; for example, 1, 3; 2, 4-dibenzylidene sorbitol, 1, 3; 2, 4-bis (p-methylbenzylidene) sorbitol, 1, 3; 2, 4-bis (3, 4-dimethylenebenzylidene) sorbitol.
The lubricant dispersant has both lubricating and dispersing functions, and according to some embodiments of the present invention, the lubricant dispersant is at least one of oxidized polyethylene wax (OPE wax), polyethylene wax (PE wax), ethylene acrylic acid wax (EAA wax). Preferably, the oxidized polyethylene wax with average relative molecular mass of 2500-3000 and average acid value of 15 is adopted.
In the raw materials, the addition of the precipitated barium sulfate can enhance and improve the hardness of the product and reduce the cost, and the influence on the glossiness of the PP surface is low, and the precipitated barium sulfate with the particle size of 2-5 mu m is generally adopted as the precipitated barium sulfate. The oxidant can adopt at least one of an antioxidant 1010 and an antioxidant 168; the oleamide may be oleamide produced by Aksunobel, the Netherlands, and the erucamide may be erucamide produced by Dasipo chemical Co., Ltd.
According to some embodiments of the present invention, the raw material further comprises 1 to 2 parts by weight of a toner.
In a second aspect of the present invention, there is provided a method for preparing any one of the scratch-resistant flame-retardant PP materials provided in the first aspect of the present invention, comprising the following steps:
s1, mixing the precipitated barium sulfate with a dispersing agent, and fully stirring and dispersing to obtain pretreated precipitated barium sulfate;
s2, uniformly mixing other raw materials with the precipitated barium sulfate pretreated in the step S1, then feeding the mixture into an extruder, and extruding and granulating the mixture to obtain the barium sulfate.
In the preparation method, the precipitated barium sulfate is pretreated, so that the phenomenon that the surface of a product generates pock spots and influences the appearance due to poor dispersion of the precipitated barium sulfate can be prevented, and the precipitated barium sulfate is polar inorganic filler and can be agglomerated together due to moisture, so that the precipitated barium sulfate can be scattered by adopting high-mixing dispersion treatment of a high-speed mixer, and in the process, the moisture can be evaporated, and the surface of the precipitated barium sulfate particles is charged with certain static electricity, so that agglomeration is prevented. Wherein the mass ratio of the dispersing agent to the precipitated barium sulfate is (30-50): 1 was added.
According to some embodiments of the invention, the extruder is a twin-screw extruder, the rotation speed is 250-450 rpm, the length-diameter ratio is 40/1, and the temperature from the feeding section to the head of the extruder is: 160 ℃ in the first zone, 170 ℃ in the second zone, 175 ℃ in the third zone, 180 ℃ in the fourth zone, 180 ℃ in the fifth zone, 185 ℃ in the sixth zone, 185 ℃ in the seventh zone, 185 ℃ in the eighth zone, 185 ℃ in the ninth zone, 190 ℃ in the head and a vacuum degree of more than 0.6 MPa.
In a third aspect of the invention, a toilet seat is provided, which is made of any one of the scratch-resistant flame-retardant PP materials provided by the first aspect of the invention.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a scratch-resistant flame-retardant PP material which can be used for preparing a toilet seat, has the characteristics of flame retardance and scratch resistance and is low in cost; the toilet seat ring prepared from the PP material has high strength, good toughness and excellent surface gloss, and can greatly attract the eyes of customers visually; in addition, the flame retardant is added into the raw materials of the PP material, and the formed PP material can enable the flame retardant grade of the toilet seat to REACH UL94V-2 grade and meet the environment-friendly requirements of ROHS and REACH; moreover, the raw materials of the PP material are added with the migrating slipping agent oleamide and erucamide, so that the surface scratch-resistant effect can be improved, the migrating slipping agent oleamide and the erucamide can be cooperated with the scratch-resistant agent, the formed PP material can greatly improve the scratch-resistant performance of the toilet seat, and the excellent scratch-resistant performance can still be maintained after the toilet seat is washed by the detergent; in addition, the oleamide and the erucamide also have an antistatic effect, so that the toilet seat made of the material is not easy to adsorb dust, hair and the like.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The scratch-resistant flame-retardant PP material is prepared by the following specific preparation method:
s1, weighing the raw materials according to the raw material ratio in the table 1;
s2, adding the precipitated barium sulfate and a dispersing agent EB-FF into a high-speed stirrer according to the mass ratio of 40:1, wherein the stirring speed is 600r/min, and the stirring time is 90S, so as to obtain pretreated precipitated barium sulfate;
s3, sequentially adding homopolymerized PP (homopolymerized polypropylene resin), pretreated precipitated barium sulfate, a flame retardant, a nucleating agent, a lubricating dispersant, an antioxidant, oleamide, erucamide, a scratch-resistant agent and toner into a high-speed stirrer, wherein the stirring speed is 300r/min, and the stirring time is 120S, so as to obtain a uniform mixture;
s4, feeding the mixture obtained in the step S3 into a double-screw extruder, wherein the double-screw extruder is a co-rotating double-screw extruder, the rotating speed is 250-450 rpm, the length-diameter ratio is 40/1, and the temperature from the feeding section to the head of the extruder is as follows: the PP material is prepared by the steps of firstly, 160 ℃, secondly, 170 ℃, thirdly, 175 ℃, fourthly, 180 ℃, fifthly, 180 ℃, sixthly, seventhly, eighthly, 185 ℃, ninth, 185 ℃ and 190 ℃ of a machine head, vacuumizing, wherein the vacuum degree is more than 0.6MPa, extruding and granulating.
TABLE 1 raw material weight ratio of PP materials of each comparative example and example
In the raw materials of the above examples and comparative examples, 1kg of the raw materials were taken in parts by weight. Wherein the particle size of the precipitated barium sulfate is 2-5 μm. The flame retardant is a bromine phosphorus nitrogen flame retardant, wherein the phosphorus content is 32%, the nitrogen content is 33%, and the bromine content is 10%; in other embodiments, other bromine phosphorus nitrogen flame retardants can be used, wherein the phosphorus content, the nitrogen content and the bromine content in the bromine phosphorus nitrogen flame retardants are 30-35%, 30-35% and 8-12%, respectively. The nucleating agent is sorbitol nucleating agent, and can be 1,3 specifically; 2, 4-dibenzylidene sorbitol, 1, 3; 2, 4-bis (p-methylbenzylidene) sorbitol, 1, 3; 2, 4-bis (3, 4-dimethylenebenzylidene) sorbitol. The lubricating dispersant adopts at least one of oxidized polyethylene wax (OPE wax), polyethylene wax (PE wax) and ethylene acrylic acid wax (EAA wax); the antioxidant adopts at least one of antioxidant 1010 and antioxidant 168; the scratch-resistant agent specifically adopts reactive high polysiloxane.
(II) Performance testing
The PP materials prepared by the above comparative examples and the examples are processed into corresponding processed samples respectively, and then performance tests are carried out. The specific method comprises the following steps:
(1) the PP materials prepared in the above comparative examples and embodiments were respectively injection molded into national standard sample strips by an injection molding machine, and tensile strength, flexural modulus, impact strength and melt index were measured.
(2) Respectively carrying out injection molding on the PP material prepared in each proportion and the embodiment by using an injection molding machine to obtain UL-94 standard flame-retardant sample bars, and testing the vertical combustion flame-retardant grade.
(3) Respectively carrying out injection molding on the PP material prepared in each proportion and the embodiment by using an injection molding machine to obtain a highlight plate with the thickness of 3mm, wherein the highlight plate is 125mm multiplied by 300mm, and testing the surface glossiness of the highlight plate by using a glossiness instrument; the high gloss panels were then tested using a five finger scratch tester, recording the force at which significant scratch marks began to develop.
(4) And (3) cleaning the high-gloss board with a detergent, drying, testing the high-gloss board with a five-finger scratch tester, and recording the force for generating obvious scratch marks.
The processed samples of the PP materials obtained in the above comparative examples and examples were tested by the above methods, and the results are shown in Table 2.
Table 2 results of performance testing
As can be seen from the above tables 1 and 2, the PP materials prepared in examples 1-6 have high flame retardant efficiency and good scratch resistance; in comparative example 1, where no slip agent (oleamide and erucamide) was added, the scratch resistance was only 2N; in comparative example 2 and comparative example 3, after each addition of oleamide and erucamide, the scratch force started to reach 5N, but after washing with the washing solution, it dropped to 3N; in comparative example 4, the initial scratch force reached 6N after the simultaneous addition of oleamide and erucamide, and also dropped to 3N after washing with the washing solution. In examples 1 to 6, after the oleamide, the erucamide and the scratch-resistant agent are added together, the force for generating scratch is increased along with the increase of the addition amount of the scratch-resistant agent; in example 4, the amounts of oleic acid amide, erucamide and the scratch-resistant agent are 0.2 part by weight, 0.2 part by weight and 2 parts by weight, respectively, the force for generating scratches reaches 10N, after the cleaning agent is washed, the force for generating scratches is kept at 8N, which is improved by 4-6N compared with the comparative examples 1-4.
Claims (10)
1. The scratch-resistant flame-retardant PP material is characterized by comprising the following raw materials in parts by weight: 70-80 parts of homopolymerized polypropylene resin, 10-20 parts of precipitated barium sulfate, 3-4 parts of flame retardant, 0.2-0.3 part of nucleating agent, 1-2 parts of lubricating dispersant, 0.2-0.5 part of antioxidant, 0.1-0.3 part of oleamide, 0.1-0.3 part of erucamide and 0.5-2 parts of scratch-resistant agent.
2. The scratch-resistant flame-retardant PP material according to claim 1, wherein the flame retardant is a bromine phosphorus nitrogen flame retardant; the bromine phosphorus nitrogen flame retardant contains 30-35% of phosphorus, 30-35% of nitrogen and 8-12% of bromine.
3. The scratch-resistant flame-retardant PP material according to claim 1, wherein the scratch-resistant agent is a reactive high polysiloxane.
4. The scratch-resistant flame-retardant PP material as claimed in claim 1, wherein the melt index of the homo-polypropylene resin at 230 ℃ and 2.16kg is 20-30 g/10 min.
5. The scratch-resistant flame-retardant PP material according to claim 1, wherein the nucleating agent is a sorbitol nucleating agent.
6. The scratch-resistant flame-retardant PP material according to claim 1, wherein the lubricating dispersant is at least one of oxidized polyethylene wax, polyethylene wax and ethylene acrylic acid wax.
7. The scratch-resistant flame-retardant PP material according to any one of claims 1 to 6, wherein the raw material further comprises 1-2 parts by weight of a toner.
8. The process for the preparation of a scratch resistant flame retardant PP material according to any of claims 1 to 7, characterized in that it comprises the following steps:
s1, mixing the precipitated barium sulfate with a dispersing agent, and fully stirring and dispersing to obtain pretreated precipitated barium sulfate;
s2, uniformly mixing other raw materials with the precipitated barium sulfate pretreated in the step S1, then feeding the mixture into an extruder, and extruding and granulating the mixture to obtain the barium sulfate.
9. The preparation method of the scratch-resistant flame-retardant PP material according to claim 8, wherein the extruder is a twin-screw extruder, the rotating speed is 250-450 rpm, the length-diameter ratio is 40/1, and the temperature from the feeding section to the head of the extruder is as follows: 160 ℃ in the first zone, 170 ℃ in the second zone, 175 ℃ in the third zone, 180 ℃ in the fourth zone, 180 ℃ in the fifth zone, 185 ℃ in the sixth zone, 185 ℃ in the seventh zone, 185 ℃ in the eighth zone, 185 ℃ in the ninth zone, 190 ℃ in the head and a vacuum degree of more than 0.6 MPa.
10. A toilet seat characterized by being made of the scratch resistant flame retardant PP material of any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010057316.XA CN111234376B (en) | 2020-01-19 | 2020-01-19 | Scratch-resistant flame-retardant PP (polypropylene) material, preparation method thereof and toilet seat ring |
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| CN202010057316.XA CN111234376B (en) | 2020-01-19 | 2020-01-19 | Scratch-resistant flame-retardant PP (polypropylene) material, preparation method thereof and toilet seat ring |
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| CN111234376A true CN111234376A (en) | 2020-06-05 |
| CN111234376B CN111234376B (en) | 2022-10-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7375589B2 (en) | 2020-02-07 | 2023-11-08 | Toto株式会社 | toilet seat |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367317A (en) * | 2011-06-24 | 2012-03-07 | 深圳市科聚新材料有限公司 | Flame retardant polypropylene (PP) material and its preparation method |
| CN109354768A (en) * | 2018-10-16 | 2019-02-19 | 青岛科技大学 | A kind of preparation of high-performance refractory scraping-resistant polypropylene material |
-
2020
- 2020-01-19 CN CN202010057316.XA patent/CN111234376B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367317A (en) * | 2011-06-24 | 2012-03-07 | 深圳市科聚新材料有限公司 | Flame retardant polypropylene (PP) material and its preparation method |
| CN109354768A (en) * | 2018-10-16 | 2019-02-19 | 青岛科技大学 | A kind of preparation of high-performance refractory scraping-resistant polypropylene material |
Non-Patent Citations (3)
| Title |
|---|
| 吴宏富等: "《中国粉体工业通鉴》", 30 June 2006, 中国建材工业出版社 * |
| 孟成铭等: ""汽车用耐刮擦改性聚丙烯的研制"", 《工程塑料应用》 * |
| 海关总署加工贸易及保税监管司编: "《加工贸易单耗标准实务手册.6》", 31 December 2011, 中国海关出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7375589B2 (en) | 2020-02-07 | 2023-11-08 | Toto株式会社 | toilet seat |
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