WO2015172270A1 - Foaming-promoting liquid potassium/zinc composite heat stabilizer for pvc wallpaper, and preparation method therefor - Google Patents
Foaming-promoting liquid potassium/zinc composite heat stabilizer for pvc wallpaper, and preparation method therefor Download PDFInfo
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- WO2015172270A1 WO2015172270A1 PCT/CN2014/000763 CN2014000763W WO2015172270A1 WO 2015172270 A1 WO2015172270 A1 WO 2015172270A1 CN 2014000763 W CN2014000763 W CN 2014000763W WO 2015172270 A1 WO2015172270 A1 WO 2015172270A1
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
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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
Definitions
- PVC wallpaper ⁇ promote foaming liquid potassium, / zinc composite heat stable fe fe!! S side Technical field
- the invention relates to a PVC heat stabilizer and a preparation method thereof, in particular to a foaming type liquid potassium/zinc composite heat stabilizer for PVC wallpaper and a preparation method thereof.
- Polyvinyl chloride (PVC) is widely used in various fields due to its excellent mechanical properties and good processing properties, as well as corrosion resistance, aging resistance, low cost, abundant raw materials and mature manufacturing processes.
- PVC Polyvinyl chloride
- PVC can be processed at temperatures above 160 °C, and it begins to thermally decompose at 120-130 °C, releasing HC1 gas. If the production of HC1 is not inhibited, the decomposition will be further aggravated.
- the selection of heat stabilizers is very important.
- the commonly used heat stabilizers for PVC mainly include lead salts, organotins, metal soaps and rare earths.
- Lead salt heat stabilizer is the earliest type of heat stabilizer. It has good long-term thermal stability and low price, but lead is a toxic substance, which is not conducive to environmental protection.
- Organotin-based heat stabilizer can be used for transparent products, but the processing It has an exciting taste, and is expensive and uncompetitive.
- Lead soap and cadmium soap in metal soap heat stabilizer have good stability but are toxic; calcium soap and barium soap have poor initial thermal stability, and initial thermal stability of zinc soap Good, but poor durability, prone to "zinc burning” phenomenon, can not be used alone; rare earth heat stabilizer, due to better comprehensive performance, has been widely used in recent years, but some of these rare earth compounds are also toxic, Affected by the shortage of rare earth resources, its price is rising, and its application is also limited.
- the object of the present invention is to overcome the deficiencies of the prior art and provide an environmentally friendly and non-toxic PVC wallpaper.
- the foaming type liquid potassium/zinc composite heat stabilizer and the preparation method thereof have the advantages of good thermal stability and foam promoting function, high foaming efficiency, high cost performance, and prior art Compared with the functional PVC heat stabilizer, it has a greater market competitive advantage.
- PVC wallpaper for promoting foaming liquid potassium/zinc composite heat stabilizer which is prepared by the following components by weight percentage: isooctanoic acid] 2.8% ⁇ 43, 3%, oleic acid 14.4% ⁇ 21.8% , benzoic acid 4.8% ⁇ 10.2%, potassium hydroxide 5.6% ⁇ 8.7%, zinc oxide 10.8% ⁇ 14.9%, solvent oil 11,6% ⁇ 44.5%, phosphite 4,9% ⁇ : 10,1%, The total amount of each of the above components was 100%.
- the PVC wallpaper uses a foam-promoting liquid potassium/zinc composite heat stabilizer, which is prepared from the following components by weight percentage: 36.8% isooctanoic acid, 21.1% oleic acid, benzoic acid 6.2%, potassium hydroxide 6.1%, zinc oxide 11.2%, solvent oil 13.5%, phosphite 5.1%.
- the solvent oil is selected from Sinopec D80 solvent oil.
- the phosphite is phosphite Markl 500.
- the invention relates to a method for preparing a foaming type liquid potassium/zinc composite heat stabilizer for PVC wallpaper, which comprises the following steps:
- the invention utilizes various organic acids to react with KOH and ZnO to form various organic potassium salts and zinc
- the salt system through a variety of different organic acid radicals and ⁇ ions, z n ions to play their own special effects, can make PVC wallpaper products have good thermal stability, and at the same time processability, compatibility, and resistance to precipitation Well, it also promotes foaming and promotes high foaming efficiency;
- the invention adopts a novel environmentally friendly, non-toxic and high-efficiency heat-resistant auxiliary phosphite Markl500 and potassium/zinc compounding, which greatly improves the heat resistance stability of the long-span;
- the composite heat stabilizer of the invention has no "three wastes" in the production process, the process is simple and easy, environmentally friendly, non-toxic, the product is transparent, the color is beautiful and has no odor, and the amount thereof can be reduced by more than half by the traditional heat stabilizer. It is especially suitable for the use of foamed PVC wallpaper produced by scraping off-paper method or rotary screen method. Compared with domestic and international functional products, it has excellent cost performance and has greater market competitive advantage.
- Example 1 The PVC wallpaper of the present embodiment was prepared by using a foam-promoting liquid potassium/zinc composite heat stabilizer from the following components by weight percentage: 12.8% isooctanoic acid, 14.4% oleic acid, 4.8% benzoic acid. Potassium hydroxide 5.6%, zinc oxide 10.8%, solvent oil D80 (Sinopec) 44.5%, phosphite Markl500 7.1%.
- Example 2 PVC foaming liquid potassium/zinc composite heat stabilizer for the PVC wallpaper of this example The following components by weight percentage were prepared: 22.7% isooctanoic acid, 21.8% oleic acid, 10.2% benzoic acid, 8.7% potassium hydroxide, 14.9% zinc oxide, solvent oil D80 (Sinopec) 11.6%, phosphite Markl500 10.1%.
- Example 3 The PVC wallpaper of the present embodiment uses a foaming type liquid potassium/zinc composite heat stabilizer, and the following weight Percentage of components were prepared: isooctanoic acid 43.3%, oleic acid 15%, benzoic acid 7%, potassium hydroxide 7%, zinc oxide 10.8%, solvent oil D80 (Sinopec) 12%, phosphite Markl500 4.9% .
- Example 4 The PVC wallpaper of the present embodiment was prepared by using a foam-promoting liquid potassium/zinc composite heat stabilizer from the following components by weight: 27% isooctanoic acid, 18% oleic acid, 7.8% benzoic acid. Potassium hydroxide 7.5%, 12.8% zinc oxide, 22% solvent oil D80 (Sinopec), 4.9% phosphite Markl500.
- Example 5 The PVC wallpaper of the present embodiment was prepared by using a foam-promoting liquid potassium/zinc composite heat stabilizer from the following components by weight: 36.8% isooctanoic acid, 21.1% oleic acid, 6.2% benzoic acid. Potassium hydroxide 6.1%, zinc oxide 11.2%, solvent oil D80 (Sinopec) 13.5%, phosphite Markl500 5.1%.
- Example 6 For comparison with the composite heat stabilizer of the present invention, the PVC heat stabilizer of the present example was prepared from the following components by weight percentage: isooctanoic acid 60.3%, diethylene glycol butyl ether 5 , 6%, potassium hydroxide 7.0%, zinc oxide 13.9 ° /. , ethylene glycol butyl ether 13.2%. The preparation steps are as follows:
- isooctanoic acid is added to dissolve potassium hydroxide and then dissolved in zinc oxide;
- the heat stabilizers prepared in Examples 1 to 6 were respectively pulled on a double roll of a refining machine according to the test standard formula and cut into pieces, and placed in an oven at 190 ⁇ 1 ° C for static heat aging test.
- the test results are shown in Table 1.
- Thermal stability test results of products 1 to 6 Thus, PVC samples (samples 1 to 5) prepared by using the foam-promoting liquid potassium/zinc composite heat stabilizer (Examples 1 to 5) of the present invention, and a prior art heat stabilizer (Examples) can be seen. 6) Compared with the prepared PVC sample (sample 6), the thermal stability is greatly improved.
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Paper (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
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Abstract
The present invention relates to a foaming-promoting liquid potassium/zinc composite heat stabilizer for PVC wallpaper, and a preparation method therefor. The foaming-promoting liquid potassium/zinc composite heat stabilizer for PVC wallpaper is prepared by using the following components in weight percentage: 12.8% to 43.3% of isocaprylic acid, 14.4% to 21.8% of oleic acid, 4.8% to 10.2% of benzoic acid, 5.6% to 8.7% of potassium hydroxide, 10.8% to 14.9% of zinc oxide, 11.6% to 44.5% of solvent naphtha and 4.9% to 10.1% of phosphite. The preparation steps are: (1) mixing isocaprylic acid, oleic acid and solvent naphtha, then adding benzoic acid at a temperature of 65ºC, adding and dissolving potassium hydroxide and then adding and dissolving zinc oxide; (2) heating to 110ºC to 120ºC and stirring for 90 minutes so as to allow a reaction to be complete until a solution is clear and transparent and has no granule; and (3) carrying out cooling to 80ºC to 90ºC, adding phosphite and carrying out thermal insulation for 30 minutes. The composite heat stabilizer of the present invention is environmentally friendly, has no toxicity, good dual functions of heat stability and foaming promotion, and has high foaming promoting efficiency, high cost performance and wide market prospects.
Description
PVC墙纸甩促发泡型液体钾, /锌复合热稳宁 fe!! S方 技术领域 PVC wallpaper 甩 promote foaming liquid potassium, / zinc composite heat stable fe fe!! S side Technical field
本发明涉及一种 PVC热稳定剂及其制备方法， 具体涉及一种 PVC墙纸 用促发泡型液体钾 /锌复合热稳定剂及其制备方法。 The invention relates to a PVC heat stabilizer and a preparation method thereof, in particular to a foaming type liquid potassium/zinc composite heat stabilizer for PVC wallpaper and a preparation method thereof.
背景技术 Background technique
聚氯乙烯 （PVC) 因具有优良的力学性能和良好的加工性能， 又兼具耐 腐蚀、 耐老化、 成本低、 原料丰富、 制造工艺成熟等特点， 而被广泛应用于 各个领域， 成为世界五大通用树脂之一。 Polyvinyl chloride (PVC) is widely used in various fields due to its excellent mechanical properties and good processing properties, as well as corrosion resistance, aging resistance, low cost, abundant raw materials and mature manufacturing processes. One of the general resins.
然而， PVC—般在 160°C以上才能加工成型， 而它在 120~130°C时就开 始热分解，释放出 HC1气体，如果不抑制 HC1的产生，分解又会进一步加剧， PVC加工过程中的热稳定剂的选用十分重要。 However, PVC can be processed at temperatures above 160 °C, and it begins to thermally decompose at 120-130 °C, releasing HC1 gas. If the production of HC1 is not inhibited, the decomposition will be further aggravated. The selection of heat stabilizers is very important.
PVC 常用热稳定剂主要有铅盐类、有机锡类、金属皂类和稀土类等。铅 盐类热稳定剂是开发最早的一类热稳定剂， 其长期热稳定性好、 价格便宜， 但铅是有毒物质， 不利于环保； 有机锡类热稳定剂可用于透明制品， 但加工 过程中有剌激性味道， 且价格昂贵， 缺乏竞争力； 金属皂类热稳定剂中铅皂、 镉皂稳定性好， 但有毒； 钙皂、 钡皂初期热稳定性差， 锌皂初期热稳定性较 好， 但持久性差， 后期易发生 "锌烧"现象， 均不能单独使用； 稀土类热稳 定剂， 由于综合性能较好， 近年来得到广泛应用， 但其中某些稀土化合物也 具有毒性， 同时受到稀土资源短缺的影响， 其价格在不断上涨， 使其应用也 受到一定限制。 The commonly used heat stabilizers for PVC mainly include lead salts, organotins, metal soaps and rare earths. Lead salt heat stabilizer is the earliest type of heat stabilizer. It has good long-term thermal stability and low price, but lead is a toxic substance, which is not conducive to environmental protection. Organotin-based heat stabilizer can be used for transparent products, but the processing It has an exciting taste, and is expensive and uncompetitive. Lead soap and cadmium soap in metal soap heat stabilizer have good stability but are toxic; calcium soap and barium soap have poor initial thermal stability, and initial thermal stability of zinc soap Good, but poor durability, prone to "zinc burning" phenomenon, can not be used alone; rare earth heat stabilizer, due to better comprehensive performance, has been widely used in recent years, but some of these rare earth compounds are also toxic, Affected by the shortage of rare earth resources, its price is rising, and its application is also limited.
因此， 需要发展一种新型 PVC热稳定剂， 不仅热稳定性好、 环保无毒， 而且性价比高。 Therefore, it is necessary to develop a new type of PVC heat stabilizer, which is not only good in thermal stability, environmentally friendly, non-toxic, but also cost-effective.
发明内容 Summary of the invention
本发明的目的是克服现有技术的不足，提供一种环保、无毒的 PVC墙纸
用促发泡型液体钾 /锌复合热稳定剂及其制备方法，本发明的热稳定剂具有良 好的热稳定性和促发泡双重功能， 促发泡效率高， 性价比高， 与现有技术同 功能的 PVC热稳定剂相比具有更大的市场竞争优势。 The object of the present invention is to overcome the deficiencies of the prior art and provide an environmentally friendly and non-toxic PVC wallpaper. The foaming type liquid potassium/zinc composite heat stabilizer and the preparation method thereof have the advantages of good thermal stability and foam promoting function, high foaming efficiency, high cost performance, and prior art Compared with the functional PVC heat stabilizer, it has a greater market competitive advantage.
本发明解决所述技术问题采用的技术方案是： The technical solution adopted by the present invention to solve the technical problem is:
PVC墙纸用促发泡型液体钾 /锌复合热稳定剂，其特征在于， 由以下重量 百分比含量的组分制备而成： 异辛酸 】2.8%〜43,3%， 油酸 14.4%〜21.8%， 苯甲酸 4.8%〜10.2%， 氢氧化钾 5.6%〜8.7%， 氧化锌 10.8%〜14.9%, 溶剂 油 11,6%〜44.5%， 亚磷酸酯 4,9%〜： 10,1%， 上述各组分的总量为 100%。 优选地， 所述的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 其特征 在于， 由以下重量百分比含量的组分制备而成：异辛酸 36.8%，油酸 21.1%， 苯甲酸 6.2%，氢氧化钾 6.1%，氧化锌 11.2%,溶剂油 13.5%,亚磷酸酯 5.1%。 进一步地， 所述溶剂油选用中石化的 D80溶剂油。 进一步地， 所述亚磷酸酯是亚磷酸酯 Markl500。 所述的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂的制备方法， 其特 征在于， 包括以下步骤： PVC wallpaper for promoting foaming liquid potassium/zinc composite heat stabilizer, which is prepared by the following components by weight percentage: isooctanoic acid] 2.8%~43, 3%, oleic acid 14.4%~21.8% , benzoic acid 4.8%~10.2%, potassium hydroxide 5.6%~8.7%, zinc oxide 10.8%~14.9%, solvent oil 11,6%~44.5%, phosphite 4,9%~: 10,1%, The total amount of each of the above components was 100%. Preferably, the PVC wallpaper uses a foam-promoting liquid potassium/zinc composite heat stabilizer, which is prepared from the following components by weight percentage: 36.8% isooctanoic acid, 21.1% oleic acid, benzoic acid 6.2%, potassium hydroxide 6.1%, zinc oxide 11.2%, solvent oil 13.5%, phosphite 5.1%. Further, the solvent oil is selected from Sinopec D80 solvent oil. Further, the phosphite is phosphite Markl 500. The invention relates to a method for preparing a foaming type liquid potassium/zinc composite heat stabilizer for PVC wallpaper, which comprises the following steps:
( 1) 将异辛酸、 油酸和溶剂油混合， 在 下加入苯甲酸， 再加入氢 氧化钾溶解后， 加入氧化锌溶解； (1) mixing isooctanoic acid, oleic acid and solvent oil, adding benzoic acid underneath, adding potassium hydroxide to dissolve, and adding zinc oxide to dissolve;
(2)升温至 110°C〜120°C， 搅拌 90分钟使反应完全， 直至溶液澄清透 明无粒状物存在； (2) The temperature is raised to 110 ° C to 120 ° C, and the reaction is completed by stirring for 90 minutes until the solution is clear and transparent and free of particulate matter;
(3) 降温至 80° ( 〜 90°C， 加入亚磷酸酯， 保温 30分钟即得成品 本发明的技术方案可以： ¾到以下有益效果： (3) Cool down to 80 ° (~ 90 ° C, add phosphite, keep warm for 30 minutes to get the finished product The technical solution of the invention can: 3⁄4 to the following beneficial effects:
( 1 ) 本发明利用多种有机酸与 KOH、 ZnO反应生成多种有机钾盐和锌
盐体系， 通过多种不同的有机酸根与 κ离子、 zn离子发挥各自不同的特殊 功效， 能使 PVC墙纸产品的热稳定性良好， 且同时加工性、 相容性、 耐压析 性均较好， 还起到促发泡作用， 促发泡效率高； (1) The invention utilizes various organic acids to react with KOH and ZnO to form various organic potassium salts and zinc The salt system, through a variety of different organic acid radicals and κ ions, z n ions to play their own special effects, can make PVC wallpaper products have good thermal stability, and at the same time processability, compatibility, and resistance to precipitation Well, it also promotes foaming and promotes high foaming efficiency;
(2) 本发明采用了新型环保、 无毒、 高效耐热助剂亚磷酸酯 Markl500 与钾 /锌复配， 大大提高了长斯耐热稳定性能； (2) The invention adopts a novel environmentally friendly, non-toxic and high-efficiency heat-resistant auxiliary phosphite Markl500 and potassium/zinc compounding, which greatly improves the heat resistance stability of the long-span;
(3)本发明的复合热稳定剂在生产过程中无"三废"产生， 工艺简单易 行， 环保、 无毒， 产品透明、 色泽漂亮无异味， 其用量可以比传统热稳定剂 减少一半以上， 特别适用于涂刮离型纸法或圆网法生产的发泡 PVC 墙纸使 用， 与国内、 国际上同功能产品相比较， 具有优异的性价比， 具有更大市场 竞争优势。 (3) The composite heat stabilizer of the invention has no "three wastes" in the production process, the process is simple and easy, environmentally friendly, non-toxic, the product is transparent, the color is beautiful and has no odor, and the amount thereof can be reduced by more than half by the traditional heat stabilizer. It is especially suitable for the use of foamed PVC wallpaper produced by scraping off-paper method or rotary screen method. Compared with domestic and international functional products, it has excellent cost performance and has greater market competitive advantage.
具体实施方式 detailed description
下面结合具体实施例对本发明作进一步的说明， 但本发明不受下述实施 例的限定。 The invention is further illustrated by the following examples, but the invention is not limited by the following examples.
实施例 1 本实施例的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 由以下重量 百分比含量的组分制备而成： 异辛酸 12.8%， 油酸 14.4%, 苯甲酸 4.8%， 氢氧化钾 5.6%, 氧化锌 10.8%， 溶剂油 D80 (中石化） 44.5%， 亚磷酸酯 Markl500 7.1%。 Example 1 The PVC wallpaper of the present embodiment was prepared by using a foam-promoting liquid potassium/zinc composite heat stabilizer from the following components by weight percentage: 12.8% isooctanoic acid, 14.4% oleic acid, 4.8% benzoic acid. Potassium hydroxide 5.6%, zinc oxide 10.8%, solvent oil D80 (Sinopec) 44.5%, phosphite Markl500 7.1%.
( 1 ) 将异辛酸、 油酸和溶剂油 D80混合， 在 65°C下加入苯甲酸， 再加
入氢氧化钾溶解后， 加入氧化锌溶解； (1) Mix isooctanoic acid, oleic acid and solvent oil D80, add benzoic acid at 65 ° C, plus After the potassium hydroxide is dissolved, zinc oxide is added to dissolve;
(2)升温至 110'C〜120°C， 搅拌 90分钟使反应完全， 直至溶液澄清透 明无粒状物存在； (2) The temperature is raised to 110 ° C to 120 ° C, and the reaction is completed by stirring for 90 minutes until the solution is clear and transparent and free of particulate matter;
(3)降温至 80°C〜90°C， 加入亚磷酸酯 Markl500，保温 30分钟即得成 口 实施例 2 本实施例的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 由以下重量 百分比含量的组分制备而成： 异辛酸 22.7%， 油酸 21.8%, 苯甲酸 10.2%， 氢氧化钾 8.7%, 氧化锌 14.9%， 溶剂油 D80 (中石化) 11.6%, 亚磷酸酯 Markl500 10.1%。 (3) Cooling to 80 ° C ~ 90 ° C, adding phosphite Markl500, holding for 30 minutes to obtain the mouth Example 2 PVC foaming liquid potassium/zinc composite heat stabilizer for the PVC wallpaper of this example, The following components by weight percentage were prepared: 22.7% isooctanoic acid, 21.8% oleic acid, 10.2% benzoic acid, 8.7% potassium hydroxide, 14.9% zinc oxide, solvent oil D80 (Sinopec) 11.6%, phosphite Markl500 10.1%.
其制备步骤如下： The preparation steps are as follows:
( 1 ) 将异辛酸、 油酸和溶剂油 D80混合， 在 65'C下加入苯甲酸， 再加 入氢氧化钾溶解后， 加入氧化锌溶解； (1) mixing isooctanoic acid, oleic acid and solvent oil D80, adding benzoic acid at 65 ° C, adding potassium hydroxide to dissolve, and adding zinc oxide to dissolve;
(2)升温至 110°C〜120°C， 搅拌 90分钟使反应完全， 直至溶液澄清透 明无粒状物存在； (2) The temperature is raised to 110 ° C to 120 ° C, and the reaction is completed by stirring for 90 minutes until the solution is clear and transparent and free of particulate matter;
(3)降温至 80eC〜90°C， 加入亚磷酸酯 Markl500， 保温 30分钟即得成 品。 (3) Cool down to 80 e C~90 ° C, add phosphite Markl500, keep warm for 30 minutes to get the finished product.
实施例 3 本实施例的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 由以下重量
百分比含量的组分制备而成： 异辛酸 43.3%， 油酸 15%, 苯甲酸 7%, 氢氧化钾 7%， 氧化锌 10.8%， 溶剂油 D80 (中石化） 12%， 亚磷酸酯 Markl500 4.9%。 Example 3 The PVC wallpaper of the present embodiment uses a foaming type liquid potassium/zinc composite heat stabilizer, and the following weight Percentage of components were prepared: isooctanoic acid 43.3%, oleic acid 15%, benzoic acid 7%, potassium hydroxide 7%, zinc oxide 10.8%, solvent oil D80 (Sinopec) 12%, phosphite Markl500 4.9% .
其制备步骤如下： The preparation steps are as follows:
( 1 ) 将异辛酸、 油酸和溶剂油 D80混合， 在 65°C下加入苯甲酸， 再加 入氢氧化钾溶解后， 加入氧化锌溶解； (1) mixing isooctanoic acid, oleic acid and solvent oil D80, adding benzoic acid at 65 ° C, adding potassium hydroxide to dissolve, and adding zinc oxide to dissolve;
(2)升温至 110。C〜120。C , 搅拌 90分钟使反应完全， 直至溶液澄清透 明无粒状物存在； (2) Warm up to 110. C~120. C, stirring for 90 minutes to complete the reaction until the solution is clear and transparent and free of particulate matter;
( 3)降温至 80°C〜90°C， 加入亚磷酸酯 Markl500， 保温 30分钟即得成 品。 (3) Cool down to 80 ° C ~ 90 ° C, add phosphite Markl500, keep warm for 30 minutes to get the finished product.
实施例 4 本实施例的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 由以下重量 百分比含量的组分制备而成： 异辛酸 27%， 油酸 18%， 苯甲酸 7.8%, 氢氧化钾 7.5%,
氧化锌 12.8%, 溶剂油 D80 (中石化） 22%, 亚磷酸酯 Markl500 4.9%。 Example 4 The PVC wallpaper of the present embodiment was prepared by using a foam-promoting liquid potassium/zinc composite heat stabilizer from the following components by weight: 27% isooctanoic acid, 18% oleic acid, 7.8% benzoic acid. Potassium hydroxide 7.5%, 12.8% zinc oxide, 22% solvent oil D80 (Sinopec), 4.9% phosphite Markl500.
其制备步骤如下： The preparation steps are as follows:
( 1 ) 将异辛酸、 油酸和溶剂油 D80混合， 在 65°C下加入苯甲酸， 再加 入氢氧化钾溶解后， 加入氧化锌溶解； (1) mixing isooctanoic acid, oleic acid and solvent oil D80, adding benzoic acid at 65 ° C, adding potassium hydroxide to dissolve, and adding zinc oxide to dissolve;
(2)升温至 110° (：〜 120°C， 搅拌 90分钟使反应完全， 直至溶液澄清透 明无粒状物存在； (2) Raise the temperature to 110 ° (: ~ 120 ° C, stir for 90 minutes to complete the reaction until the solution is clear and transparent and free of particulate matter;
( 3 )降温至 80° (〜 90°C， 加入亚磷酸酯 Markl500， 保温 30分钟即得成 (3) Cool down to 80 ° (~ 90 ° C, add phosphite Markl500, keep warm for 30 minutes
P P
实施例 5 本实施例的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 由以下重量 百分比含量的组分制备而成： 异辛酸 36.8%, 油酸 21.1%, 苯甲酸 6.2%, 氢氧化钾 6.1%， 氧化锌 11.2%， 溶剂油 D80 (中石化） 13.5%, 亚磷酸酯 Markl500 5.1%。 Example 5 The PVC wallpaper of the present embodiment was prepared by using a foam-promoting liquid potassium/zinc composite heat stabilizer from the following components by weight: 36.8% isooctanoic acid, 21.1% oleic acid, 6.2% benzoic acid. Potassium hydroxide 6.1%, zinc oxide 11.2%, solvent oil D80 (Sinopec) 13.5%, phosphite Markl500 5.1%.
其制备步骤如下： The preparation steps are as follows:
( 1 ) 将异辛酸、 油酸和溶剂油 D80混合， 在 65'C下加入苯甲酸， 再加 入氢氧化钾溶解后， 加入氧化锌溶解；
(2)升温至 110eC〜120°C， 搅拌 90分钟使反应完全， 直至溶液澄清透 明无粒状物存在； (1) mixing isooctanoic acid, oleic acid and solvent oil D80, adding benzoic acid at 65 ° C, then adding potassium hydroxide to dissolve, adding zinc oxide to dissolve; (2) The temperature is raised to 110 e C~120 ° C, and the reaction is completed by stirring for 90 minutes until the solution is clear and transparent and free of particles;
(3 )降温至 80°C〜90°C，加入亚磷酸酯 Markl500， 保温 30分钟即得成 (3) Cool down to 80 ° C ~ 90 ° C, add phosphite Markl500, keep warm for 30 minutes
PP
BO。 BO.
实施例 6 用于与本发明的复合热稳定剂作对比试验， 本实施例的 PVC热稳定剂， 由以下重量百分比含量的组分制备而成： 异辛酸 60.3%， 二乙二醇丁醚 5,6% , 氢氧化钾 7.0% ， 氧化锌 13.9°/。 ， 乙二醇丁醚 13.2%。 其制备步骤如下： Example 6 For comparison with the composite heat stabilizer of the present invention, the PVC heat stabilizer of the present example was prepared from the following components by weight percentage: isooctanoic acid 60.3%, diethylene glycol butyl ether 5 , 6%, potassium hydroxide 7.0%, zinc oxide 13.9 ° /. , ethylene glycol butyl ether 13.2%. The preparation steps are as follows:
( 1 ) 在 80°C下， 异辛酸加入氢氧化钾溶解后加入氧化锌溶解； (1) at 80 ° C, isooctanoic acid is added to dissolve potassium hydroxide and then dissolved in zinc oxide;
(2) 升温至 105 左右搅拌 30 分钟使反应完全， 至溶液变清无细粒氧 化锌存在； (2) The temperature is raised to about 105 and stirred for 30 minutes to complete the reaction until the solution becomes clear and no fine-grained zinc oxide exists;
(3 )在溶液中滴加氢氧化钾， 保持温度在 110°C左右， 加入乙二醇丁醚 脱水， 脱水后加入助剂搅拌 15 分钟即可。 (3) Add potassium hydroxide dropwise to the solution, keep the temperature at about 110 °C, add dehydrated ethylene glycol butyl ether, and add the auxiliary agent for 15 minutes after dehydration.
实施例 7 热稳定性测试 Example 7 Thermal Stability Test
分别用实施例 1〜6制备的热稳定剂按照试验标准配方在炼塑机双辊上拉 片并裁剪制成样片， 放入 190±1 °C烤箱中进行静态耐热老化试验。 试验结果 见表 1。
品 1〜6的热稳定性测试结果
由此可见， 用本发明的促发泡型液体钾 /锌复合热稳定剂 （实施例 1〜5) 制备出来的 PVC样片 （样品 1〜5)， 与采用现有技术热稳定剂 （实施例 6) 制备出的 PVC样片 （样品 6) 相比， 热稳定性大大提高。 The heat stabilizers prepared in Examples 1 to 6 were respectively pulled on a double roll of a refining machine according to the test standard formula and cut into pieces, and placed in an oven at 190 ± 1 ° C for static heat aging test. The test results are shown in Table 1. Thermal stability test results of products 1 to 6 Thus, PVC samples (samples 1 to 5) prepared by using the foam-promoting liquid potassium/zinc composite heat stabilizer (Examples 1 to 5) of the present invention, and a prior art heat stabilizer (Examples) can be seen. 6) Compared with the prepared PVC sample (sample 6), the thermal stability is greatly improved.
最后应说明的是： 以上仅为本发明的优选实施例而已， 并不用于限制本 发明， 尽管参照实施例对本发明进行了详细的说明， 对于本领域的技术人员 来说， 其依然可以对前述实施例所记载的技术方案进行修改， 或者对其中部 分技术特征进行等同替换， 但是凡在本发明的精神和原则之内， 所作的任何 修改、 等同替换、 改进等， 均应包含在本发明的保护范围之内。
It should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art can still The technical solutions described in the embodiments are modified, or equivalent modifications are made to some of the technical features, but any modifications, equivalent substitutions, improvements, etc., which are made within the spirit and principles of the present invention, are included in the present invention. Within the scope of protection.
Claims
1、 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 其特征在于， 由以下重量 百分比含量的组分制备而成： 1. PVC-based foam-promoting liquid potassium/zinc composite heat stabilizer, which is characterized by being composed of the following components by weight percentage:
异辛酸 12.8%〜43.3%， Isooctanoic acid 12.8%~43.3%,
油酸 14.4%〜21.8°/。， Oleic acid 14.4%~21.8°/. ,
苯甲酸 4.8%〜10.2%， Benzoic acid 4.8%~10.2%,
氢氧化钾 5.6%〜8.7%， Potassium hydroxide 5.6%~8.7%,
氧化锌 10.8%〜14.9%， Zinc oxide 10.8%~14.9%,
溶剂油 11.6%〜44.5%, Solvent oil 11.6%~44.5%,
亚磷酸酯 4.9%〜； 10.1%， Phosphite 4.9%~; 10.1%,
上述各组分的总量为 100%。 The total amount of each of the above components is 100%.
2、根据权利要求 1所述的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂， 其 特征在于， 由以下重量百分比含量的组分制备而成： The foam-promoting liquid potassium/zinc composite heat stabilizer for PVC wallpaper according to claim 1, which is characterized in that it is prepared from the following components by weight percentage:
异辛酸 36.8%， Isooctanoic acid 36.8%,
油酸 21.1%， Oleic acid 21.1%,
苯甲酸 6.2%， Benzoic acid 6.2%,
氢氧化钾 6.1%, Potassium hydroxide 6.1%,
氧化锌 11.2%， Zinc oxide 11.2%,
溶剂油 13.5%,
Solvent oil 13.5%,
3、 根据权利要求 1或 2所述的 PVC墙纸用促发泡型液体钾 /锌热稳定剂， 其 特征在于， 所述溶剂油选用中石化的 D80溶剂油。 The foam-promoting liquid potassium/zinc heat stabilizer for PVC wallpaper according to claim 1 or 2, wherein the solvent oil is selected from Sinopec D80 solvent oil.
4、 根据权利要求 1或 2所述的 PVC墙纸用促发泡型液体钾 /锌热稳定剂， 其 特征在于， 所述亚磷酸酯是亚磷酸酯 Markl500。 The foam-promoting liquid potassium/zinc heat stabilizer for PVC wallpaper according to claim 1 or 2, wherein the phosphite is phosphite Markl500.
5、根据权利要求 1或 2所述的 PVC墙纸用促发泡型液体钾 /锌复合热稳定剂 的制备方法， 其特征在于， 包括以下步骤： The method for preparing a foam-promoting liquid potassium/zinc composite heat stabilizer for PVC wallpaper according to claim 1 or 2, comprising the steps of:
( 1 ) 将异辛酸、 油酸和溶剂油混合， 在 65°C下加入苯甲酸， 再加入氢 氧化钾溶解后， 加入氧化锌溶解； (1) mixing isooctanoic acid, oleic acid and solvent oil, adding benzoic acid at 65 ° C, adding potassium hydroxide to dissolve, and adding zinc oxide to dissolve;
(2)升温至 110°C〜120'C， 搅拌 90分钟使反应完全， 直至溶液澄清透 明无粒状物存在； (2) The temperature is raised to 110 ° C to 120 ° C, and the reaction is completed by stirring for 90 minutes until the solution is clear and transparent and free of particulate matter;
( 3) 降温至 80°C〜90°C， 加入亚磷酸酯， 保温 30分钟即得成品。
(3) Cool down to 80 ° C ~ 90 ° C, add phosphite, keep warm for 30 minutes to get the finished product.
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| CN104004295B (en) * | 2014-05-12 | 2015-09-02 | 广州市联诺化工科技有限公司 | PVC wallpaper is with inspiring alveolitoid Liquid K/Zn composite thermal stabilizer and preparation method thereof |
| CN104499357B (en) * | 2014-11-19 | 2017-04-12 | 广州市联诺化工科技有限公司 | Paste for PVC (polyvinyl chloride) foaming wallpaper, PVC foaming wallpaper and preparation method thereof |
| CN106700313A (en) * | 2015-11-16 | 2017-05-24 | 上海欣旺壁纸有限公司 | Wall paper high-foaming slurry and preparation method thereof |
| CN105821713B (en) * | 2016-03-16 | 2018-02-02 | 黄山佳仕居装饰材料有限公司 | A kind of production method of plastic relief PVC wallpaper |
| CN106543584A (en) * | 2016-10-31 | 2017-03-29 | 江苏昊晟塑业科技有限公司 | Automotive trim panel is heat-resisting to use expanded material |
| CN106589681B (en) * | 2016-12-05 | 2019-02-26 | 浙江传化华洋化工有限公司 | A kind of PVC facilitates bubble stabilizer and preparation method thereof with urea rouge/biuret groups Liquid K zinc |
| CN112898632A (en) * | 2019-12-07 | 2021-06-04 | 嘉兴若天新材料科技有限公司 | Colorless, odorless and environment-friendly liquid stabilizer for transparent hose |
| CN111205514A (en) * | 2020-03-12 | 2020-05-29 | 德清县东来化学有限公司 | Sodium potassium zinc liquid stabilizer and preparation method and application thereof |
| CN115232358A (en) * | 2022-07-28 | 2022-10-25 | 佛山众塑通新材料技术有限公司 | Liquid potassium-zinc composite stabilizer for PVC (polyvinyl chloride) foaming pad and preparation method thereof |
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