CN109942889B - Phosphate-containing composition and application thereof - Google Patents
Phosphate-containing composition and application thereof Download PDFInfo
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- CN109942889B CN109942889B CN201910236220.7A CN201910236220A CN109942889B CN 109942889 B CN109942889 B CN 109942889B CN 201910236220 A CN201910236220 A CN 201910236220A CN 109942889 B CN109942889 B CN 109942889B
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Abstract
The invention relates to a warpage preventing composition containing phosphate and application thereof, wherein the warpage preventing composition contains the phosphate and a second component, the phosphate is 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) sodium phosphate or bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] aluminum phosphate, the second component is selected from one or more of p-tert-butyl aluminum hydroxy benzoate, sodium benzoate and hydrated magnesium silicate, and the weight ratio of the phosphate to the second component is 1: (0.1-10), wherein the warpage of the product prepared from the polymer is less than or equal to 3%.
Description
Technical Field
The invention belongs to the field of polymer additives, and particularly relates to a phosphate-containing anti-warping composition and application thereof, in particular to a polymer containing the anti-warping composition, wherein the polymer has lower warping degree.
Background
Warpage is the deviation of the shape of the injection molded article from the shape of the mold cavity, which is one of the common defects of plastic articles. With the development of the plastic industry, people have higher and higher requirements on the appearance and the service performance of plastic products, and the degree of warpage is also more and more concerned and emphasized by mold designers as one of important indexes for evaluating the quality of products. The mold designer hopes to predict the reason of warping of the plastic part in the design stage so as to optimize the design, thereby improving the efficiency and quality of injection molding production, shortening the design period of the mold and reducing the cost. The addition of the anti-warping auxiliary agent in the current anti-warping measures is a main approach.
For example, CN105400173A discloses a polymer with low warpage and high hardness, wherein the POK resin comprises 40-80% of POK resin, 0.1-2% of compatilizer, 0.1-5% of processing aid and 20-60% of glass fiber, the preparation method is strict through the steps of material preparation, mixing and extrusion, the material selection is scientific, and the prepared polymer has more excellent impact resistance and low warping degree compared with the conventional engineering plastics and is suitable for occasions with high precision requirements.
Also, CN103013173A discloses a pigment composition with anti-warping property in plastics, which is prepared by adding a derivative in which two meta-positions or two meta-positions and para-positions on the benzene ring of DPP structure are substituted by long-chain alkyl, alkoxy or alkylthio groups, thereby improving the anti-warping property of the pigment in plastics.
CN102933649A discloses a polypropylene stiffening nucleating agent composition, which is prepared by mixing aluminum hydroxy p-tert-butylbenzoate and sodium benzoate, or by mixing aluminum hydroxy p-tert-butylbenzoate and/or sodium benzoate with sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate or aluminum [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate. The nucleating agent composition can improve the bending property, the impact strength and the heat distortion temperature of a polypropylene product, and has the characteristics of small addition amount, stable chemical property and good dispersibility in polypropylene.
For example, CN101845171A discloses a polypropylene stiffening nucleating agent composition, which is prepared by mixing p-tert-butyl aluminum hydroxy benzoate and sodium benzoate, or alternatively, the composition is prepared by mixing p-tert-butyl aluminum hydroxy benzoate and/or sodium benzoate and sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate or aluminum bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate; the nucleating agent composition can obviously improve the bending property, the impact strength, the heat distortion temperature and the like of a PP product, and the modified PP product can stand long-term high temperature and mechanical stress, thereby being very suitable for application in the field of outdoor special materials such as daily life products, medical appliances, electric appliances, automobiles, pipe pipelines and the like.
For example, CN102219927A discloses a polypropylene stiffening and toughening nucleating agent composition, which comprises a carboxylate nucleating agent and a phosphate nucleating agent, wherein the carboxylate nucleating agent is selected from one or more of sodium benzoate and aluminum hydroxy p-tert-butylbenzoate, the phosphate nucleating agent is selected from any one of sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate and aluminum bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate, and the nucleating agent composition breaks through the limitation that the original single nucleating agent cannot simultaneously improve the impact strength and flexural modulus of polypropylene, and can significantly improve not only the flexural modulus and the heat distortion temperature of a polypropylene product, but also the impact strength.
However, no plastic additive capable of preventing warpage well has been found, and the present invention has found out aids capable of preventing warpage, which show excellent effects in preventing warpage.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a use of a warpage-preventing composition comprising a phosphate for reducing warpage of a polymer, wherein the warpage-preventing composition comprises a phosphate and a second component, the phosphate is 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) sodium phosphate or bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] aluminum phosphate, the second component is one or more selected from p-tert-butyl aluminum hydroxy benzoate, sodium benzoate, and hydrated magnesium silicate, and the weight ratio of the phosphate to the second component is 1: (0.1-10).
Preferably, the weight ratio of the phosphate to the second component is (1-4): (1-4).
Preferably, in the above-mentioned application, the warpage prevention composition can enable an article made of the polymer to have a warpage of 3% or less.
Preferably, in the above use, the polymer is polyethylene or polypropylene.
Preferably, in the above use, the total weight of the phosphate and the second component in the composition is 10-100% by weight of the composition.
Preferably, in the above use, the second component is p-tert-butyl aluminum hydroxy benzoate, sodium benzoate or hydrous magnesium silicate.
Preferably, in the above use, the second component is any two or three of p-tert-butyl aluminium hydroxy benzoate, sodium benzoate and hydrous magnesium silicate.
Preferably, in the above polymer pellets, the warpage preventing composition comprises a phosphate and a second component, wherein the phosphate is sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate or aluminum bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate, the second component is one or more selected from the group consisting of p-tert-butyl aluminum hydroxy benzoate, sodium benzoate and hydrated magnesium silicate, and the weight ratio of the phosphate to the second component is 1: (0.1-10).
Preferably, in the polymer pellets, the polymer pellets are obtained by mixing, melting and granulating a polymer raw material and an anti-warping composition, wherein the polymer raw material is polyethylene or polypropylene, the anti-warping composition accounts for 0.01 to 0.5 weight percent of the polymer pellets, and the warping degree of the polymer pellets after being prepared into a polymer product is less than or equal to 3 percent.
Preferably, in the polymer pellet, the second component is p-tert-butyl aluminum hydroxy benzoate, sodium benzoate or hydrous magnesium silicate, or the second component is any two or three of p-tert-butyl aluminum hydroxy benzoate, sodium benzoate and hydrous magnesium silicate.
The invention also provides a low-warpage polymer product, which is prepared from the polymer granules.
The invention also provides a warping-preventing composition, which comprises a phosphate and a second component, wherein the phosphate is 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) sodium phosphate or bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] aluminum phosphate, the second component is selected from one or more of p-tert-butyl aluminum hydroxy benzoate, sodium benzoate and hydrated magnesium silicate, and the weight ratio of the phosphate to the second component is 1: (0.1-10).
The invention has the advantages of
The anti-warping composition of the present invention has been developed specifically for solving the warping problem of polymers, and at the same time, has achieved a new use of the above-mentioned composition of the present invention, which has not been used previously to specifically solve the anti-warping aspect, and has now been found to be capable of achieving the solving of the warping problem of polymers. And the warp-proof effect is good, and the warp degree of the polymer can be reduced to below 3%.
In the warping composition, the problem of warping cannot be solved by a single component, a phosphate component and a second component are required to be jointly used for solving the problem of warping, and the absolute synergistic effect of warping prevention is realized between the phosphate and other components.
Detailed Description
Example 1 preparation of anti-warping composition
The raw materials are mixed according to the components and the weight percentage content of the anti-warping composition, and then the mixture is fully and uniformly stirred, so that the anti-warping composition from A1 to A8 is obtained.
TABLE 1 composition of anti-warping compositions
Example 2 Polymer with Low warpage
The preparation method of the polymer comprises the following steps:
5 single-component sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate, aluminum bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate, aluminum p-tert-butylbenzoate, sodium benzoate and magnesium silicate hydrate, the blank polypropylene and the above-mentioned warpage-preventing compositions A1-A8 were mixed with polypropylene, respectively, the amount of the single-component and warpage-preventing compositions added was 0.1% by weight of the polypropylene, and the blank polypropylene was not added with any component. Then, the melt granulation was carried out by using a twin-screw extruder, respectively, to obtain polypropylene pellets, respectively.
The method for measuring the warping degree comprises the following steps:
600g of polypropylene pellets containing a single component, polypropylene pellets containing no component and polypropylene pellets containing A1-A8 described above were each injection-molded in an injection molding machine into a disk having a diameter of 15cm and a thickness of 2.5cm, which was kept at 90 ℃ in hot water for 30 minutes and left at room temperature for 24 hours, tested 10 times repeatedly, and the warpage of 10 injection-molded parts was measured and averaged.
The specific measurement method comprises the following steps: the longitudinal shrinkage is the molding shrinkage parallel to the melt flow direction, the transverse shrinkage is the molding shrinkage perpendicular to the melt flow direction, and then the warpage is calculated according to the formula of warpage | longitudinal shrinkage/transverse shrinkage-1 | h 100% ", and the understanding of the calculation method can refer to the Chinese standard GB/T17037.4-2003.
TABLE 2 warpage of Polypropylene articles comprising an anti-warpage component
TABLE 3 warpage of Polypropylene articles comprising an anti-warpage composition
| Composition numbering | The composition is added in | Warping degree (%) |
| A1 | 0.1％ | 2.45 |
| A2 | 0.1％ | 2.78 |
| A3 | 0.1％ | 2.31 |
| A4 | 0.1％ | 2.15 |
| A5 | 0.1％ | 2.44 |
| A6 | 0.1％ | 2.73 |
| A7 | 0.1％ | 2.56 |
| A8 | 0.1％ | 2.48 |
As can be seen from the warpage test in Table 2, the warpage of the polymer product is high and is above 10% when sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate and aluminum bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate are used alone, whereas the warpage of the polymer product is above 4% when aluminum hydroxy-tert-butylbenzoate, sodium benzoate and hydrous magnesium silicate are used alone, and the warpage is 7.8% when no auxiliary agent is added to the polymer.
As can be seen from the warpage test in table 3, the addition of the same total amount of the composition can achieve the effect that the phosphate improves the warpage indexes of the p-tert-butyl aluminum hydroxy benzoate, sodium benzoate and hydrous magnesium silicate, and the warpage is reduced by the high warpage component, which fully reflects the excellent characteristics of the composition containing the phosphate in warpage prevention, and the effect of synergy can be seen when the sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate and the aluminum bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate are mixed with the p-tert-butyl aluminum hydroxy benzoate, sodium benzoate and hydrous magnesium silicate.
Claims (5)
1. Use of an anti-warp composition comprising a phosphate salt and a second component, wherein the phosphate salt is sodium 2, 2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate or aluminum bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) ] phosphate, the second component is selected from one or more of aluminum hydroxy-p-tert-butylbenzoate, sodium benzoate and hydrated magnesium silicate, and the weight ratio of the phosphate salt to the second component is 1: (0.1-10).
2. Use according to claim 1, characterized in that the anti-warping composition is capable of providing an article made of polypropylene with a warp of 3% or less.
3. Use according to claim 1, characterized in that the total weight of phosphate and second component in the composition is 10-100% by weight of the composition.
4. Use according to claim 1, characterized in that the second component is hydroxy aluminium p-tert-butylbenzoate, sodium benzoate or magnesium silicate hydrate.
5. Use according to claim 1, characterised in that the second component is any two or three of hydroxy aluminium p-tert-butylbenzoate, sodium benzoate and magnesium silicate hydrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004083852A (en) * | 2002-06-24 | 2004-03-18 | Asahi Denka Kogyo Kk | Nucleating agent and crystalline polymer composition containing the same |
| CN100537643C (en) * | 2002-10-08 | 2009-09-09 | 电气化学工业株式会社 | Heat-schrinkable film |
| CN101942146B (en) * | 2009-07-10 | 2012-06-27 | 中国石油化工股份有限公司 | Controllable rheological high-gloss polypropylene resin and preparation method thereof |
| CN101845171A (en) * | 2010-04-20 | 2010-09-29 | 广州呈和科技有限公司 | Polypropylene reinforcement nucleating agent composition |
| CN108641192A (en) * | 2018-06-21 | 2018-10-12 | 刘强 | A kind of production method of complex polypropylene resin new material |
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