WO2018228201A1 - 一种砜聚合物组合物及其应用 - Google Patents

一种砜聚合物组合物及其应用 Download PDF

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Publication number
WO2018228201A1
WO2018228201A1 PCT/CN2018/089117 CN2018089117W WO2018228201A1 WO 2018228201 A1 WO2018228201 A1 WO 2018228201A1 CN 2018089117 W CN2018089117 W CN 2018089117W WO 2018228201 A1 WO2018228201 A1 WO 2018228201A1
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Prior art keywords
polymer composition
additive
sulfone polymer
hindered phenol
phosphite
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PCT/CN2018/089117
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English (en)
French (fr)
Inventor
代惊奇
高红军
陈锐斌
龙杰明
孙学科
曹民
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金发科技股份有限公司
珠海万通特种工程塑料有限公司
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Publication of WO2018228201A1 publication Critical patent/WO2018228201A1/zh

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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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a sulfone polymer composition and a thermoplastic molding composition composed thereof and an application thereof.
  • Sulfone polymer is a special high temperature resistant transparent thermoplastic engineering plastic, mainly including polysulfone PSU, polyethersulfone PES and polyphenylenesulfone PPSU. It has excellent mechanical properties, high rigidity, wear resistance, high strength, high thermal stability, and high glass transition temperature of about 190 °C. Excellent mechanical properties even at high temperatures, long-term use temperature of 160 ° C, short-term use temperature of 190 ° C, and hydrolysis resistance, good dimensional stability, small molding shrinkage, non-toxic, radiation-resistant, flame-resistant, self-extinguishing It has excellent electrical properties, chemical stability and resistance to general acids, bases and salts in a wide temperature range.
  • the production process has now become a well-known technique in which a polymer is produced by electrophilic substitution reaction using a solution polymerization method, and the solvent used is generally a high-boiling protic solvent, such as Sulfolane or N-methylpyrrolidone, the monomers used include dihalophenyl sulfone and dihydroxy phenol or phenyl sulfone.
  • the alkali metal or alkali metal compound is used as a salt forming agent to convert the hydroxy group into a phenolate group and then with a halogen end group. condensation.
  • the produced polymer solution is filtered, pulverized, purified, and dried to obtain a polymer powder or fine particles. It is preferred to carry out melt granulation through a twin-screw extruder or a single-screw extruder to obtain yellowish transparent resin particles.
  • sulfone polymers are highly sensitive polymers that are prone to cross-linking degradation or external environmental dust and other contaminants that cause blackening, reduced transparency, bubbles, or contaminated spots.
  • crystal points are due to the chemical reaction of branching or cross-linking of the polymer backbone, or the incorporation of some tiny foreign matter, which causes the refractive index to change and the appearance difference; the bubbles are due to the volatilization of small molecules.
  • Small molecules may be produced by decomposition of compounds such as additives with low temperature resistance.
  • the sulfone polymer is sensitive to additives, and the product is prone to deformation, distortion, pressure cracking and the like when the amount of the additive is too large or the amount of the additive is too large, thereby reducing the service life of the product.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a sulfone polymer composition which can effectively avoid generation of crystal spots and bubbles while solving the problem of oxidative discoloration.
  • a sulfone polymer composition consisting of the following components:
  • polysulfone polyethersulfone, polyphenylenesulfone
  • the heat resistance of the phosphite additive and the hindered phenol additive is characterized by thermogravimetric analysis (TGA), and the weight loss at 360 ° C is not more than 10%; wherein the hindered phenol additive accounts for the sum of the mass of the phosphite additive and the hindered phenol additive. 1 to 50%.
  • TGA thermogravimetric analysis
  • the additive should be selected to satisfy the sulfone polymer without deterioration at higher processing temperatures, and the processing temperature of the sulfone polymer is about 360 ° C, so the additive should have good high temperature resistance.
  • the invention selects a phosphite additive with high heat resistance level, and simultaneously adds a hindered phenol additive with excellent thermal stability, and the additive is not easily decomposed at a high temperature to solve the problem of bubble generation.
  • the resistance to yellowing and aging of materials is often improved by the addition of hindered phenolic antioxidants.
  • the hydrogen bond and the ether bond on the benzene ring are easily attacked by oxygen radicals, which leads to molecular chain branching and degradation.
  • the mechanism of action of the hindered phenol antioxidant is that the phenolic hydroxyl group can easily provide proton trapping radicals. Inactivation; the mechanism of action of the phosphite is to decompose the hydroperoxide while terminating the peroxy radical and the alkoxy radical.
  • the inventors have found that the addition of these two additives to the sulfone polymer produces a synergistic effect, which refers to hindered phenol as the primary antioxidant and phosphite as the secondary antioxidant , the former capturing peroxy radicals and inhibiting polymerization.
  • Branching and degrading of molecular chains prevents the formation of crystal points, and also cuts off the chain reaction of oxidative degradation of polymers; the latter has redox characteristics, on the one hand, it can decompose hydroperoxides in polymers to form inactive products such as alcohol ketones.
  • the oxidized phenolic antioxidant can be reduced, and itself is oxidized to form a colorless or white phosphate compound, which can minimize the color change of the polymer and improve the color stability of the product. Therefore, the synergistic effect of the hindered phenol and the phosphite makes the anti-yellowing effect more obvious.
  • the quality of the hindered phenol additive can play a good synergistic effect when it accounts for 1 to 50% of the total mass of the phosphite additive and the hindered phenol additive.
  • the sulfone polymer when the sulfone polymer is thermally oxidized, the benzene ring H in the ortho position of the ether bond will generate more hydroperoxide.
  • the content of the hindered phenolic additive is too high, the sulfone polymer is easily formed. Green, so when the content of the hindered phenol additive is appropriate, it can effectively play the role of anti-oxidation and discoloration, and at the same time avoid the generation of crystal points and bubbles, and obtain a resin product with uniform color and purity.
  • the hindered phenol additive comprises 10 to 30% of the total mass of the phosphite additive and the hindered phenol additive.
  • the sulfone polymer composition comprises a total content of the phosphite additive and the hindered phenol additive in an amount of from 100 ppm to 5000 ppm by weight of the sulfone polymer composition.
  • the polysulfone, polyethersulfone, polyphenylenesulfone has the following structure:
  • structural formula I is polysulfone PSU
  • structural formula II is polyethersulfone PES
  • structural formula III is polyphenylenesulfone PPSU, wherein n is 10 to 500.
  • the phosphite additive is a monoalkyl and/or dialkyl substituted aromatic phosphite.
  • the phosphite additive is tetrakis(2,4-di-tert-butylphenyl)[1,1'-diphenyl]-4,4'-diphosphite, diphosphoric acid (2) One or two of 4-tetra-tert-butylphenyl pentaerythritol esters.
  • the hindered phenol additive is tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid]pentaerythritol ester, 1,3,5-tris(4-tert-butyl-3-hydroxy- 2,6-Dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4,6-tris(3,5-di-tert-butyl) One or more of -4-hydroxybenzyl)benzene.
  • the crystal point or bubble size was measured according to the ASTM 3351-93 method, and the sample was molded by an injection molding machine with a size of 200*200*0.5 mm.
  • the sulfone polymer composition is processed into various articles by a general molding process, including one or more of injection molding, compression molding, blow molding, and extrusion molding.
  • the sulfone polymer composition may be subjected to blending modification, including one or several of dyeing, filling, and fiber reinforced; the dyeing is dyeing with organic and/or inorganic toner; The filling is filled with an inorganic material; the fiber reinforcement is fiber reinforced with glass fibers and/or carbon fibers.
  • the sulfone polymer composition is used in the fields of food safety, household appliances, medical care, electronic appliances, aerospace or energy and chemical engineering.
  • the present invention has the following beneficial effects:
  • the additive phosphite has a beneficial effect on inhibiting the yellowing of the sulfone polymer product, but does not mention the problem of changes in the crystal point and the bubble.
  • the inventors found that phosphites have problems of easy hydrolysis and high temperature resistance, which not only adversely affect the transparency of the resin, but also have difficulty in achieving the appearance of the patent publication, and when the amount of addition increases, significant crystal spots and bubbles are generated. .
  • the invention selects a phosphite additive with high heat resistance level, and simultaneously adds a hindered phenol additive with excellent thermal stability, and by adjusting the ratio of the two additives, it can avoid generation of crystal points and bubbles, and can effectively play Antioxidant discoloration.
  • PEPQ tetrakis(2,4-di-tert-butylphenyl)[1,1'-diphenyl]-4,4'-diphosphite
  • dioctadecyl diphosphite pentaerythritol ester dioctadecyl diphosphite pentaerythritol ester
  • 608 bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite
  • S-9228 bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite
  • S-9228 contains hundreds of ppm of the hydrolysis inhibitor triisopropanolamine.
  • the extruder used was a D25mm type Berstorff twin-screw extruder, which was subjected to compound extrusion at a melting temperature of about 300 to 350 ° C.
  • the additive was pre-mixed in the resin powder and then added to the extrusion.
  • the melt extrusion was carried out in the extruder, the extruder feed amount was 35 kg/h, the screw rotation speed was about 250 rpm, and the extrusion temperature was as shown in Table 2.
  • the colorimetric plate was prepared using a 50-ton KraussMaffei injection molding machine with a swatch thickness of 0.5 mm and a size of 200 mm * 200 mm.
  • the mildest process is used to avoid discoloration caused by overheating of the melt or excessive shearing.
  • the melting temperature is about 300-360 ° C
  • the back pressure is about 5 MPa
  • the screw speed is 50 rpm
  • the total cycle time is not higher than 30 s.
  • the blends used prior to molding were dried at 150 ° C for 4 h.
  • the injection molding machine process is shown in Table 3.
  • Injection temperature Shot °C Rear, °C Central, °C Front, °C 340 330 320 320 position Three sections Second paragraph One section / Injection pressure 125bar 120bar 120bar / Holding pressure / 50bar 50bar / compress time 8s Cooling time 12s / Mold temperature 180 ° C Screw speed 200rpm /
  • Crystal point or bubble SP-Y-1700-B fisheye measuring projector manufactured by SUNPLUS Company of Canada was tested in accordance with ASTM 3351-93, magnified 8 times, and the crystal hole size of the standard hole was recorded, and ⁇ 0.8 was recorded respectively. Mm, 0.4 to 0.8 mm, 0.2 to 0.4 mm, and the number of ⁇ 0.2 mm.
  • the crystal point is distinguished from the bubble: if the fish eye is a relatively regular circle and the boundary is clearly considered to be a bubble, it is considered to be a crystal point.
  • Transmittance, haze Detected by a light transmittance/haze meter manufactured by Shanghai Shenguang Instrument Factory, according to ASTM D-1003 on an injection molded swatch with a thickness of 2 mm.
  • L value means whiteness or brightness, the higher the whiter, the positive value of a value indicates red, negative The value indicates green, a positive b value indicates yellow, and a negative value indicates blue.
  • the upper layer of xylene is returned to the system; the temperature is maintained in the range of 200 ° C to 210 ° C.
  • the collected water volume is close to the theoretical value (540 g)
  • the reflux is continued for another 20 minutes, and no water drops are observed.
  • the salt formation was complete, and the xylene was further distilled and discharged, and the polymerization was gradually started to 230 ° C.
  • the viscosity began to increase.
  • the slope of the viscosity growth curve was substantially zero, indicating that the viscosity of the system was completely constant, and the reaction was terminated.
  • the additives PEPQ and 1790 were added to the PPSU resin powder in a weight ratio of 2:1, mixed with a high-speed mixer for 10 minutes to ensure uniform mixing, and then melt-granulated by a single-screw extruder to obtain plastic particles of the sulfone polymer composition.
  • the total amount of the additive is 5,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • the preparation process conditions were the same as those in Example 1.
  • Polyphenylene sulfone PPSU was prepared, and the additives PEPQ and 1330 were added to the PPSU resin powder in a weight ratio of 1:1, and mixed by a high-speed mixer for 10 minutes to ensure uniform mixing, and then single-screw extrusion.
  • the machine was subjected to melt granulation to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • Example 2 Prepare the process conditions as in Example 1 to prepare polyphenylene sulfone PPSU, add the additives PEPQ and 1010 to the PPSU resin powder in a weight ratio of 99:1, mix with a high speed mixer for 10 minutes to ensure uniform mixing, and then use single screw extrusion.
  • the machine was subjected to melt granulation to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 500 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • the preparation conditions were the same as in Example 1.
  • the raw material monomer 4,4'-dihydroxydiphenyl sulfone was changed to 6.849 kg (30 mol) of 2,2'-bis(4-hydroxyphenyl)propane (BPA), and the preparation was carried out.
  • Additives 608 and 1330 were added to the PSU resin powder in a weight ratio of 2:1, mixed with a high-speed mixer for 10 minutes to ensure uniform mixing, and then melt-granulated by a single-screw extruder to obtain plastic particles of the sulfone polymer composition. Wherein the total content of the additive is 100 ppm by weight of the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • the preparation conditions were the same as in Example 1.
  • the raw material monomer 4,4'-dihydroxydiphenyl sulfone was changed to 7.508 kg (30 mol) of 4,4'-dihydroxydiphenyl sulfone, and the obtained resin was polyether sulfone PES.
  • the additives S-9228 and 1790 were added to the PES resin powder in a weight ratio of 4:1, mixed with a high-speed mixer for 10 minutes to ensure uniform mixing, and then melt-granulated by a single-screw extruder to obtain a sulfone polymer composition plastic.
  • the particles, wherein the total additive content is 4000 ppm by weight of the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • Preparative process conditions were the same as in Example 5 to prepare polyethersulfone PES, and the additives S-9228 and 1330 were added to the PES resin powder in a weight ratio of 3:1, mixed with a high speed mixer for 10 minutes to ensure uniform mixing, and then squeezed with a single screw.
  • the mixture was subjected to melt granulation to obtain sulfone polymer composition plastic particles in which the total content of the additive was 2000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property. The test results are shown in Tables 4-6.
  • Example 2 Prepare the process conditions as in Example 1 to prepare polyphenylene sulfone PPSU, add the additives PEPQ and 1330 to the PPSU resin powder in a weight ratio of 7:3, mix with a high-speed mixer for 10 minutes to ensure uniform mixing, and then use single-screw extrusion.
  • the machine was subjected to melt granulation to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • Example 2 Prepare the process conditions as in Example 1 to prepare polyphenylene sulfone PPSU, add the additives PEPQ and 1330 to the PPSU resin powder in a weight ratio of 9:1, mix with a high-speed mixer for 10 minutes to ensure uniform mixing, and then use single-screw extrusion.
  • the machine was subjected to melt granulation to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 and 5.
  • the preparation conditions were the same as those in Example 1.
  • Polyphenylene sulfone PPSU was prepared, and the additives PEPQ and 1330 were added to the PPSU resin powder in a weight ratio of 99:1, and mixed by a high-speed mixer for 10 minutes to ensure uniform mixing, followed by single-screw extrusion.
  • the machine was subjected to melt granulation to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • the preparation process conditions were the same as those in Example 1.
  • Polyphenylene sulfone PPSU was prepared, and the additives PEPQ and 1330 were added to the PPSU resin powder in a weight ratio of 1:1, and mixed by a high-speed mixer for 10 minutes to ensure uniform mixing, and then single-screw extrusion.
  • the machine was subjected to melt granulation to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 5000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • the preparation process conditions were the same as those in Example 1.
  • Polyphenylene sulfone PPSU was prepared, and the additives PEPQ and 1330 were added to the PPSU resin powder in a weight ratio of 1:1, and mixed by a high-speed mixer for 10 minutes to ensure uniform mixing, and then single-screw extrusion.
  • the machine was subjected to melt granulation to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 100 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • Example 2 Prepare the PPSU resin in the same manner as in Example 2, and add phosphite 618, dioctadecyl diphosphite, to the PPSU resin powder, and mix with a high-speed mixer for 10 minutes to ensure uniform mixing.
  • the single-screw extruder was subjected to melt granulation to obtain sulfone polymer composition plastic particles in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property. The test results are shown in Tables 4-6.
  • the preparation process conditions were the same as in Example 2 to prepare a PPSU resin, and the additive 1330 was added to the PPSU resin powder.
  • the mixture was mixed for 10 minutes in a high-speed mixer to ensure uniform mixing, and then melt-granulated by a single-screw extruder to obtain plastic particles of a sulfone polymer composition, wherein the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • PPSU resin was prepared in the same manner as in Example 2.
  • the additive PEPQ was added to the PPSU resin powder, mixed with a high-speed mixer for 10 minutes to ensure uniform mixing, and then melt-granulated by a single-screw extruder to obtain a sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • PPSU resin was prepared in the same manner as in Example 2, and the additives PEPQ and 1330 were added to the PPSU resin powder in a weight ratio of 5:6, mixed by a high-speed mixer for 10 minutes to ensure uniform mixing, and then melted by a single-screw extruder. Granulation was carried out to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition. The swatch is then melted by an injection molding machine. The prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • the preparation conditions were the same as those in Example 2 to prepare PPSU resin.
  • the additives PEPQ and 1330 were added to the PPSU resin powder in a weight ratio of 3:5, mixed with a high-speed mixer for 10 minutes to ensure uniform mixing, and then melted by a single-screw extruder.
  • Granulation was carried out to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition.
  • the swatch is then melted by an injection molding machine.
  • the prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.
  • PPSU resin was prepared in the same manner as in Example 2, and additives 618 and 1330 were added to the PPSU resin powder in a weight ratio of 1:1, mixed with a high-speed mixer for 10 minutes to ensure uniform mixing, and then melted by a single-screw extruder. Granulation was carried out to obtain plastic particles of a sulfone polymer composition in which the total content of the additive was 3,000 ppm by weight based on the sulfone polymer composition. The swatch is then melted by an injection molding machine. The prepared transparent plate was used for the index test of the crystal point and the bubble and the yellowing property, and the results are shown in Tables 4 to 6.

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Abstract

本发明公开了一种砜聚合物组合物及其应用。所述砜聚合物组合物包括：聚砜、聚醚砜、聚亚苯基砜中的一种、亚磷酸酯添加剂和受阻酚添加剂；所述亚磷酸酯添加剂和受阻酚添加剂耐热性能用热失重分析(TGA)表征，360℃的失重量不高于10％。其中，受阻酚添加剂占亚磷酸酯添加剂和受阻酚添加剂质量总和的1～50％。本发明制备的砜聚合物组合物可应用于食品安全、家用电器、医疗卫生、电子电器、航空航天或能源化工领域中。

Description

一种砜聚合物组合物及其应用 技术领域
本发明涉及高分子材料技术领域，具体涉及一种砜聚合物组合物及由其组成的热塑性模塑组合物与应用。
背景技术
砜聚合物属特种耐高温透明热塑性工程塑料，主要包括聚砜PSU，聚醚砜PES和聚亚苯基砜PPSU三种类型。其力学性能优异，刚性大，耐磨，高强度，热稳定性高，具有较高的玻璃化转变温度，约为190℃。即使在高温下也保持优良的力学性能，长期使用温度为160℃，短期使用温度190℃，且耐水解，尺寸稳定性好，成型收缩率小，无毒，耐辐射，耐燃，有自熄性，在宽广的温度范围内有优良的电性能、化学稳定性，能耐一般酸，碱，盐。因此，长期以来在电子电器、机械加工、汽车、医疗器具、食品加工及不沾涂料等领域得到广泛的应用。特别是食品接触和医疗卫生方面，对材料的要求越来越高，其中一项最突出的要求就是作为可视视窗，需砜聚合物浅色，透明，纯净无异色点，例如眼镜，咖啡机视窗，婴幼奶瓶等。
砜聚合物自上世纪七十年代开发以来，其生产工艺现已成为公知技术，即用溶液聚合方法通过亲电取代反应生产高聚物，所使用的溶剂一般为高沸点的质子型溶剂，如环丁砜或N-甲基吡咯烷酮，所用单体包括二卤苯砜和二羟基苯酚或苯砜，以碱金属或碱金属化合物为成盐剂，先将羟基转化为酚盐基，再与卤素端基缩合。生产的聚合物溶液经过过滤、粉碎、纯化和干燥后得到聚合物粉末或细小颗粒。最好经过双螺杆挤出机或单螺杆挤出机进行熔融造粒，得到微黄色透明的树脂颗粒。事实上，砜聚合物是对热很敏感的高聚物，其受热后很容易发生交联降解或外界环境粉尘等污染物的影响导致发黑色，透明度下降，气泡，或有异色污染点的外观性能变化，在挤出机中熔融剪切混合时，这种现象更为严重，即使采用最温和的熔体加工处理工艺和加工生产环境也难以维持原来的外观色泽，因此，相关技术人员致力于开发在合成或熔融挤出过程中加入必要的添加剂以得到色泽均匀纯净的树脂产品。
随着透明砜聚合物的广泛应用，透明稳定的砜聚合物的开发越来越受到技术人员的重视，早在1975年即有专利GB1398133A公布了在砜聚合物中加入亚磷酸酯添加剂以增加聚合物的耐热性能和透明度的报道，至2003年前后，又公布了专利如US2003011501，US2003011502及WO2004058870公布的具有降低的黄度和高透光率性能的聚芳醚砜组合物，包括PSU、PES 和PPSU，加入的抗氧化剂只有亚磷酸酯这一种类型，另外还添加少量染料和荧光增白剂。以上公布的专利和本发明人的长期研究证明，亚磷酸酯对抑制黄变的确具有有益的作用，但未提及晶点和气泡的变化问题。发明人经过长期研究发现，亚磷酸酯由于存在易水解，耐温不够高及与树脂基体的相容性差等问题，不但对树脂的透明度具有不利影响，很难达到专利公布的外观效果，而且添加量增加时最终产生明显晶点和气泡等不良结果。一般认为，晶点的产生是因为高分子主链发生了支化或交联的化学反应，或者一些微小异物的混入，使得折光率发生变化而产生外观差异；气泡是因为小分子的挥发，这些小分子可能是耐温性能较低的添加剂等化合物分解产生的。另外，砜聚合物对添加剂比较敏感，添加剂种类过多或添加量过大时产品容易发生变形、扭曲、压力脆裂等问题，降低产品的使用寿命。
发明内容
本发明的目的是克服现有技术存在的不足，提供一种砜聚合物组合物，能有效避免产生晶点和气泡，同时解决氧化变色的问题。
本发明的上述目的通过以下技术方案予以实现：
一种砜聚合物组合物，由以下组分组成：
聚砜、聚醚砜、聚亚苯基砜中的一种；
亚磷酸酯添加剂；
受阻酚添加剂；
所述亚磷酸酯添加剂和受阻酚添加剂的耐热性能用热失重分析(TGA)表征，360℃的失重量不高于10％；其中受阻酚添加剂占亚磷酸酯添加剂和受阻酚添加剂质量总和的1～50％。
添加剂的选择要能够满足砜聚合物在较高加工温度下不会发生变质降解，而砜聚合物的加工温度约360℃，故添加剂应具有良好的耐高温性。本发明选择耐热等级高的亚磷酸酯添加剂，同时复配添加热稳定性优良的受阻酚添加剂，高温时添加剂不易分解从而解决产生气泡问题。在通用塑料和工程塑料领域中经常通过添加受阻酚类抗氧化剂来改善材料的耐黄变和耐老化效果。在砜聚合物中，苯环上的氢键和醚键均易被氧自由基进攻进而导致分子链支化、降解，受阻酚抗氧剂的作用机理是酚羟基易提供质子捕捉自由基使其失活；亚磷酸酯的作用机理是分解氢过氧化物同时又终止过氧自由基和烷氧自由基。发明人发现在砜聚合物中加入这两种添加剂可产生协同作用，所述协同作用是指受阻酚作为主抗氧剂而亚磷酸酯作为辅助抗氧剂 ，前者捕获过氧自由基，抑制聚合物分子链支化、降解，阻止晶点产生，也切断聚合 物氧化降解连锁反应；后者则具有氧化还原特性，一方面可以分解聚合物中的氢过氧化物生成醇酮等不活泼产物，另一方面可以还原被氧化的酚类抗氧剂，而本身被氧化后生成无色或白色磷酸酯类化合物，能最大限度地抑制高聚物的色泽变化，改善制品的色泽稳定性。因此，受阻酚和亚磷酸酯发生协同效应而使抗黄化效果更加明显。
经发明人研究发现，受阻酚添加剂质量占亚磷酸酯添加剂和受阻酚添加剂质量总和的1～50％时才能发挥较好的协同效果。一方面砜聚合物受热氧化时，其醚键邻位的苯环H会较多地生成氢过氧化物，另一方面如果受阻酚类添加剂含量过高则容易形成醌类物质使砜聚合物显绿色，因此受阻酚添加剂含量恰当时则既能有效地起到抗氧化变色的作用，同时还可以避免产生晶点和气泡，得到色泽均匀、纯净透明的树脂产品。
优选地，所述受阻酚添加剂占亚磷酸酯添加剂和受阻酚添加剂质量总和的10～30％。
所述砜聚合物组合物包含的亚磷酸酯添加剂和受阻酚添加剂的总含量占砜聚合物组合物按重量计算为100ppm～5000ppm。
所述聚砜、聚醚砜、聚亚苯基砜为以下结构:
Figure PCTCN2018089117-appb-000001
其中结构式I为聚砜PSU，结构式II为聚醚砜PES，结构式III为聚亚苯基砜PPSU，其中n为10～500。
所述亚磷酸酯添加剂为单烷基和/或二烷基取代的芳香族亚磷酸酯。
优选地，所述亚磷酸酯添加剂为四(2,4-二叔丁基苯基)[1,1’-二苯基]-4,4’-二亚磷酸酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯中的一种或两种。
所述受阻酚添加剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、4,6-三(3,5-二叔丁基-4-羟基苄基)苯中的一种或多种。
所述晶点或气泡大小按照ASTM3351-93方法进行测定，样品用注塑机成型指标，尺寸为200*200*0.5mm。
所述砜聚合物组合物采用通用成型工艺加工成各种制件，包括注塑成型、压塑成型、吹塑成型、挤出成型中的一种或多种。
所述砜聚合物组合物可进行共混改性，所述共混改性包括染色、填充、纤维增强中的一种或几种；所述染色为采用有机和/或无机色粉进行染色；所述填充采用无机物进行填充；所述纤维增强采用玻璃纤维和/或碳纤维进行纤维增强。
所述砜聚合物组合物在食品安全、家用电器、医疗卫生、电子电器、航空航天或能源化工领域中的应用。
与现有技术相比，本发明具有如下有益效果：
现有技术中，添加剂亚磷酸酯对抑制砜聚合物制品黄变具有有益的作用，但未提及晶点和气泡的变化问题。发明人经过长期研究发现，亚磷酸酯由于存在易水解、耐高温不够的问题，不但对树脂的透明度造成不利的影响，难以达到专利公布的外观效果，而且添加量增加时产生明显晶点和气泡。本发明选择耐热等级高的亚磷酸酯添加剂，同时复配添加热稳定性优良的受阻酚添加剂，通过调节两种添加剂的配比，既能避免产生晶点和气泡，同时可以有效地起到抗氧化变色的作用。
具体实施方式
下面结合具体实施例对本发明进行进一步解释说明，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制，但凡采用等同替换或等效变换的形式所获得的技术方案，均应包括在本发明权利要求的保护范围之内。
以下实施例和对比例所用原料均为市购。
热失重采用德国Netzsch公司TG 209F3型热重分析仪进行TGA测试，测试条件为：N 2气氛，以20℃/min速率升温至500℃。表1列出了这两类添加剂热失重数据：
表1 添加剂的热失重
亚磷酸酯型号 PEPQ 608 S-9228 618
360℃失重(％) 9.2 6.3 7.9 43.6
受阻酚型号 1790 1330 1010  
360℃失重(％) 9.5 6.8 9.9  
PEPQ：四(2,4-二叔丁基苯基)[1,1’-二苯基]-4,4’-二亚磷酸酯；
618：二亚磷酸二(十八烷基)季戊四醇酯；
608：二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯；
S-9228：二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯；
608和S-9228的主要成分相同，区别在于S-9228含数百ppm级抗水解剂三异丙醇胺。
1790：1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮；
1330：4,6-三(3,5-二叔丁基-4-羟基苄基)苯；
1010：四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯。
以下实施例和对比例中，所用挤出机为D25mm型Berstorff双螺杆挤出机，在约300～350℃熔融温度下进行混配挤出，添加剂在树脂粉末中先预混合均匀后再加入挤出机中熔融挤出，挤出机喂料量为35kg/h，螺杆转速约250rpm，挤出温度如表2所示。
表2 挤出机熔融挤出温度
机筒 机筒1 机筒2 机筒3 机筒4 机筒5 机筒6 机筒7 机筒8 机头
温度℃ 200 280 300 330 300 300 320 330 340
比色板采用50吨的KraussMaffei注塑机制备，色板厚0.5mm，大小为200mm*200mm。使用尽量温和的工艺避免熔体过热或剪切过强导致的变色，熔融温度约300～360℃，背压约5MPa且螺杆转速50rpm，总循环时间不高于30s。在模塑之前所用共混物均在150℃下干燥4h。注塑机工艺如表3所示。
表3 注塑机工艺
注塑温度 射嘴，℃ 后部，℃ 中部，℃ 前部，℃
  340 330 320 320
位置 三段 二段 一段 /
注射压力 125bar 120bar 120bar /
保压压力 / 50bar 50bar /
保压时间 8s 冷却时间 12s /
模温 180℃ 螺杆转速 200rpm /
性能测试方法：
晶点或气泡：采用加拿大SUNPLUS公司生产的SP-Y-1700-B型鱼眼测定投影仪按照ASTM 3351-93方法进行样品测试，放大8倍，对比标准孔记录晶点大小，分别记录≥0.8mm，0.4～0.8mm，0.2～0.4mm，＜0.2mm的个数。
晶点与气泡区分：如果鱼眼为较规整的圆形且边界清晰被认为是气泡，否则被认为是晶点。
透光率，雾度：用上海申光仪器厂生产的透光度/雾度测定仪，根据ASTM D-1003在厚度为2mm的注塑色板上检测。
Lab值：用美国Color I 7000A型色差仪，根据CIE规定的方法，用白色标准色板作为背景进行测试，L值表示白度或亮度，越高说明越白，a值正值表示红色，负值表示绿色，b值正值表示黄色，负值表示蓝色。
实施例1
在装有温度计、通氮气管、冷凝分水器、搅拌器的50L聚合釜中依次加入5.586kg(30mol)的4,4’-二羟基联苯，8.787kg(30.6mol)的4,4’-二氯二苯砜、再加入32.62kg的环丁砜，搅拌并升温至100℃溶解单体至溶液透明，加入3.396kg(32.039mol)成盐剂Na 2CO 3和132.6g(0.961mol)成盐剂K 2CO 3，随后加入2L二甲苯，继续搅拌下升温至成盐反应开始，体系中产生的水与二甲苯生成的共沸物被保护气吹出至冷凝管中冷凝滴下至分水器中分层，上层的二甲苯又回流至体系中；维持温度在200℃～210℃的范围，当收集水量接近理论值(540g)时，再继续回流20分钟，观察不到有水珠落下，证明成盐完全，再蒸馏并放出二甲苯，逐渐升温至230℃开始聚合反应，此时检测到粘度开始增大，恒温2.5小时后，粘度增长曲线斜率基本为零，说明体系粘度完全恒定，结束反应；停止搅拌和加热，把物料缓慢倒入无离子水中冷却成白色条状固体，再用粉碎机破碎成粉末状，用无离子水煮沸1小时，过滤去水分，如此重复10次，直至滤液用硝酸银检测不变浑浊，说明粉末中副产物盐洗除干净，过滤后把聚合物用真空烘箱120℃干燥至恒重，即得聚亚苯基砜PPSU。将添加剂PEPQ和1790用2:1的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为5000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例2
制备工艺条件同实施例1制备聚亚苯基砜PPSU，将添加剂PEPQ和1330用1:1的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例3
制备工艺条件同实施例1制备聚亚苯基砜PPSU，将添加剂PEPQ和1010用99:1的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进 行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为500ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例4
制备工艺条件同实施例1，将原料单体4,4’-二羟基二苯砜更换为6.849kg(30mol)的2,2’-双(4-羟基苯基)丙烷(BPA)，制备得到聚砜PSU。将添加剂608和1330用2:1的重量比加入PSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为100ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例5
制备工艺条件同实施例1，将原料单体4,4’-二羟基二苯砜更换为7.508kg(30mol)的4,4’-二羟基二苯砜，制备的树脂为聚醚砜PES。将添加剂S-9228和1790用4:1的重量比加入PES树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为4000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例6
制备工艺条件同实施例5制备出聚醚砜PES，将添加剂S-9228和1330用3:1的重量比加入PES树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为2000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，测试结果如表4～6所示。
实施例7
制备工艺条件同实施例1制备聚亚苯基砜PPSU，将添加剂PEPQ和1330用7:3的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例8
制备工艺条件同实施例1制备聚亚苯基砜PPSU，将添加剂PEPQ和1330用9:1的重量 比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4和5所示。
实施例9
制备工艺条件同实施例1制备聚亚苯基砜PPSU，将添加剂PEPQ和1330用99:1的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例10
制备工艺条件同实施例1制备聚亚苯基砜PPSU，将添加剂PEPQ和1330用1:1的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为5000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
实施例11
制备工艺条件同实施例1制备聚亚苯基砜PPSU，将添加剂PEPQ和1330用1:1的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为100ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
对比例1
制备工艺条件同实施例2制备出PPSU树脂，挤出造粒过程中不加添加剂。性能测试见表4～6所示。
对比例2
制备工艺条件同实施例2制备出PPSU树脂，将亚磷酸酯618，即二亚磷酸二(十八烷基)季戊四醇酯加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，测试结果如表4～6所示。
对比例3
制备工艺条件同实施例2制备出PPSU树脂，将添加剂1330加入PPSU树脂粉末中，。用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
对比例4
制备工艺条件同实施例2制备出PPSU树脂，将添加剂PEPQ加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
对比例5
制备工艺条件同实施例2制备出PPSU树脂，将添加剂PEPQ和1330用5:6的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
对比例6
制备工艺条件同实施例2制备出PPSU树脂，将添加剂PEPQ和1330用3:5的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
对比例7
制备工艺条件同实施例2制备出PPSU树脂，将添加剂618和1330用1:1的重量比加入PPSU树脂粉末中，用高速搅拌机混合10分钟以保证混合均匀，再用单螺杆挤出机进行熔融造粒，得到砜聚合物组合物塑胶粒子，其中添加剂总含量占砜聚合物组合物按重量计算为3000ppm。再用注塑机熔融制备色板。用所制备的透明色板进行晶点和气泡以及黄变性能的指标测试，结果如表4～6所示。
表4 晶点测试总表
Figure PCTCN2018089117-appb-000002
表5 气泡测试总表
Figure PCTCN2018089117-appb-000003
表6 透明测试
Figure PCTCN2018089117-appb-000004
从表4、表5、表6中的性能测试表明，实施例相较于对比例，晶点和气泡显著减少，且抗氧化变色的性能也有所提高。

Claims (10)

  1. 一种砜聚合物组合物，其特征在于，由以下组分组成：
    聚砜、聚醚砜、聚亚苯基砜中的一种；
    亚磷酸酯添加剂；
    受阻酚添加剂；
    所述亚磷酸酯添加剂和受阻酚添加剂的耐热性能用热失重分析(TGA)表征，360℃的失重量不高于10％；其中受阻酚添加剂占亚磷酸酯添加剂和受阻酚添加剂质量总和的1～50％。
  2. 根据权利要求1所述砜聚合物组合物，其特征在于，所述受阻酚添加剂占亚磷酸酯添加剂和受阻酚添加剂质量总和的10～30％。
  3. 根据权利要求1所述砜聚合物组合物，其特征在于，所述砜聚合物组合物包含的亚磷酸酯添加剂和受阻酚添加剂的总含量占砜聚合物组合物按重量计算为100ppm～5000ppm。
  4. 根据权利要求1所述砜聚合物组合物，其特征在于，所述聚砜、聚醚砜、聚亚苯基砜结构式如下：
    Figure PCTCN2018089117-appb-100001
    其中结构式I为聚砜PSU，结构式II为聚醚砜PES，结构式III为聚亚苯基砜PPSU；其中n为10～500。
  5. 根据权利要求1所述砜聚合物组合物，其特征在于，所述亚磷酸酯添加剂为单烷基和/或二烷基取代的芳香族亚磷酸酯。
  6. 根据权利要求5所述砜聚合物组合物，其特征在于，所述亚磷酸酯添加剂为四(2,4-二叔丁基苯基)[1,1’-二苯基]-4,4’-二亚磷酸酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯中的一种或两种。
  7. 根据权利要求1所述砜聚合物组合物，其特征在于，所述受阻酚添加剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、4,6-三(3,5-二叔丁基-4-羟基苄基)苯中的一种或多种。
  8. 根据权利要求1所述砜聚合物组合物，其特征在于，所述砜聚合物组合物采用通用成型工艺加工成制件，包括注塑成型、压塑成型、吹塑成型、挤出成型中的一种或多种。
  9. 根据权利要求1所述砜聚合物组合物，其特征在于，所述砜聚合物组合物可进行共混改性，所述共混改性包括染色、填充、纤维增强中的一种或几种；所述染色采用有机和/或无机色粉进行染色；所述填充采用无机物进行填充；所述纤维增强采用玻璃纤维和/或碳纤维进行纤维增强。
  10. 权利要求1～9中任一权利要求所述砜聚合物组合物在食品安全、家用电器、医疗卫生、电子电器、航空航天或能源化工领域中的应用。
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