WO2018040093A1 - 一种包含山梨醇三缩醛和单缩醛的透明成核剂组合物 - Google Patents
一种包含山梨醇三缩醛和单缩醛的透明成核剂组合物 Download PDFInfo
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Definitions
- the present invention relates to the use of a nucleating agent for preparing a polymer and a nucleating agent thereof, and more particularly to a nucleating agent composition comprising sorbitol triacetal, sorbitol diacetal and monoacetal, and a process for the preparation thereof.
- the sorbitol nucleating agent currently used in the industry is basically based on diacetal as a basic component, separating the triacetal product and monoacetal as impurities from the product, or controlling the reaction conditions during the preparation process. No triacetal or monoacetal is produced.
- the nucleating agent is purified by the method disclosed in Chinese Patent Application No. CN200410026622.8, wherein monomethylenebenzylidene sorbitol and trimethylenebenzylidene sorbitol are removed, so that the purity of the product is improved, but the patent CN200410026622. In the case of 8, the purity of the treated product cannot be 100%, and it is impossible to determine what kind of impurities are present and what the content of the impurities is.
- the content of the triacetal contained in the sorbitol nucleating agent may be too high, or the content of the triacetal may not be, for example, the preparation method of the nucleating agent disclosed in Chinese Patent Application No. CN200810219978.1, which is prepared
- the amount of aromatic aldehyde added is controlled, and the reaction time and temperature are controlled. Since the reaction sequence does not carefully control the order of addition and the amount of feed, the products of diacetal and triacetal in the reaction product cannot be controlled, and it is unclear.
- the exact range of product content range, and the effect of a nucleating agent containing a specific amount of triacetal on the properties of the product was not found.
- the present invention has been made to solve the above technical problems, and the present invention proposes a nucleating agent composition capable of containing sorbitol triacetal and monoacetal in a specific ratio with sorbitol diacetal, which is realized in a polymer.
- a special role played in the nucleation process.
- the specific role of nucleating agents containing different concentrations of sorbitol triacetal and monoacetal in different polymer nucleation processes was determined.
- a nucleating agent refers to a nucleating preparation for nucleation of a polymer.
- the present invention provides a nucleating agent composition comprising a compound of formula (I), a compound of formula (II), a compound of formula (III) and a compound of formula (IV):
- n in the formula (I), the formula (II), the formula (III) and the formula (IV) is 1 or 2;
- R is selected from a C 1 -C 8 alkyl group, a C 1 -C 4 alkoxycarboxy group, a hydroxyl group, Hydrogen, halogen and C 1 -C 6 alkylthio group, the weight ratio of the weight of the compound of the formula (I), the weight of the compound of the formula (II) to the sum of the weights of the compounds of the formula (III) and the formula (IV) in the composition is :(97.00-99.90): (0.20-8.00): (0.02-1.00).
- the ratio by weight of the compound of formula (I), the weight of the compound of formula (II) to the sum of the weights of the compounds of formula (III) and formula (IV) is: (97.00-99.90): (0.20-5.00): (0.02 -0.80).
- the weight ratio of the compound of the formula (I), the weight of the compound of the formula (II) to the sum of the weights of the compounds of the formula (III) and the formula (IV) is: (97.00-99.90): (0.20-3.00): (0.02 -0.15).
- R is -Cl, -Br, -CH 3 or -CH 2 -CH 3 .
- the present invention provides a composition comprising a compound of the above formula (I), a compound of the formula (II), a compound of the formula (III) and a compound of the formula (IV).
- the compound represented by the formula (I) is abbreviated as sorbitol diacetal, and the compound represented by the formula (II) is abbreviated as sorbitol triacetal, a compound represented by the formula (III) and the formula (IV). Referred to as sorbitol monoacetal.
- the present invention provides a method for preparing the above nucleating agent composition, the method comprising the steps of:
- step 4) heating the product of step 3) to cyclohexane reflux for aldol condensation dehydration, and maintaining heating for 0.4-1.0 hours
- step 6) heating the product of step 5) for 0.4-1.0 hours to obtain a heated mixture
- the aromatic aldehyde is of the following structural formula:
- n is 1 or 2
- R is selected from the group consisting of C 1 -C 8 alkyl, C 1 -C 4 alkoxy, carboxy, hydroxy, hydrogen, halogen, and C 1 -C 6 alkylthio.
- the composite catalyst is a mixture comprising p-toluenesulfonic acid and an alcohol ether.
- the volume ratio of the cyclohexane added in the step 5) to the cyclohexane added in the step 1) is 1:3, and the volume ratio of the cyclohexane added in the step 7) to the cyclohexane added in the step 1) is 1 :3, and the volume of the cyclohexane added in the step 5) and the step 7) is the same.
- the aromatic aldehyde is p-chlorobenzaldehyde, p-bromobenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, 3,4 dimethylbenzaldehyde, 3,4 diethylbenzaldehyde, 3,4 Chlorobenzaldehyde or 3,4 dibromobenzaldehyde.
- the acid ether composite catalyst is a mixture comprising p-toluenesulfonic acid and an alcohol ether
- the alcohol ether is an ether of ethylene glycol, preferably ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol monobutyl ether or ethylene glycol dibutyl ether, particularly preferably the alcohol ether is ethylene glycol methyl ether.
- the molar ratio of p-toluenesulfonic acid to alcohol ether in the mixture is 3-5:8-10.
- the present invention also provides the use of the nucleating agent composition prepared above for the preparation of a polymer having improved properties, wherein the polymer is polyethylene or polypropylene, and the properties include lowering the extrusion temperature, Improve transparency, gloss, flexural modulus and/or tensile strength of polymer films, polymer sheets and polymer molded articles, improve heat distortion temperature and/or dimensional stability of polymer articles, and shorten polymer articles One or more of a molding cycle and an increase in production efficiency of a polymer article.
- the present invention provides the use of the nucleating agent composition prepared above for the preparation of a polymer having improved properties, wherein the polymer is polyethylene or polypropylene, and the improved properties include (a) reduced extrusion. Temperature, (b) improve transparency, (c) increase gloss, (d) increase flexural modulus, (e) increase tensile strength, (f) increase heat distortion temperature (g), increase dimensional stability, (h) Shortening the molding cycle and (i) increasing one or more of the production efficiency of the polymer product.
- the improved properties include (a) reduced extrusion. Temperature, (b) improve transparency, (c) increase gloss, (d) increase flexural modulus, (e) increase tensile strength, (f) increase heat distortion temperature (g), increase dimensional stability, (h) Shortening the molding cycle and (i) increasing one or more of the production efficiency of the polymer product.
- the present invention provides the use of the above nucleating agent composition in the preparation of a polymer having improved clarity and reduced extrusion temperature.
- the polymer form is a polymer film, a polymer sheet, a polymer molded article or a polymer article.
- the present invention also provides a method of preparing a polymer having improved properties, the method comprising the step of adding the above nucleating agent composition to a polymer.
- the polymer is polyethylene or polypropylene
- the performance is to lower the extrusion temperature and improve the transparency, gloss, flexural modulus and/or stretching of the polymer film, the polymer sheet and the polymer molded article.
- the strength one or more of increasing the heat distortion temperature and/or dimensional stability of the polymer article, shortening the molding cycle of the polymer article, and increasing the production efficiency of the polymer product.
- the present invention also provides a process for preparing a polymer having improved properties, which comprises adding the above nucleating agent composition to a polymer which does not contain the above nucleating agent composition of the present invention to obtain a polymer having improved properties, wherein
- the polymer is polyethylene or polypropylene having (a) reduced extrusion temperature and (b) increased transparency compared to the starting polymer to which the nucleating agent composition of the invention is not added. (c) Increased gloss, (d) increased flexural modulus, (e) increased tensile strength, (f) improved product heat distortion temperature (g) improved dimensional stability, (h) shortened molding cycle, (i) at least one of improved performance in increased polymer product production efficiency.
- the improved performance is increased transparency and/or reduced extrusion temperature.
- the polymer form of the improved performance is a polymer film, a polymer sheet, a polymer molded article or a polymer article.
- the improved property is to increase the bending mode of the polymer film, the polymer sheet or the polymer molded article. Amount and tensile strength.
- the improved polymer morphology is a polymeric article, the improved properties are increased heat distortion temperature and/or increased dimensional stability.
- the present invention also provides a process for preparing a polymer having improved clarity and reduced extrusion temperature, comprising the step of adding the above transparent nucleating agent composition of the present invention to a polymer.
- the polymer is polyethylene or polypropylene.
- the present invention provides a polymer composition comprising a polymer and the above nucleating agent composition, wherein the weight percentage of the nucleating agent composition in the polymer composition is from 0.03 to 0.3%, preferably The weight percentage of the nucleating agent composition in the polymer composition is from 0.05 to 0.25%.
- the polymer is polyethylene or polypropylene.
- the polyethylene of the present invention includes, but is not limited to, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene copolymer.
- ethylene copolymers include, but are not limited to, ethylene-propylene copolymers, EVA, ethylene-butene copolymers, ethylene-octene copolymers, ethylenically unsaturated ester copolymers, and the like.
- the polypropylene of the present invention is selected from the group consisting of isotactic polypropylene, random polypropylene, syndiotactic polypropylene, chlorinated polypropylene, and grafted polypropylene.
- the above nucleating agent composition of the present invention has a particular improvement in certain properties of PE (polyethylene) and PP (polypropylene), in particular, it can reduce the processing temperature of PE and PP, and contains sorbitol triacetal and sorbitol.
- the nucleating agent of monoacetal is reduced by 10 ° C or higher relative to pure sorbitol diacetal or a transparent nucleating agent containing no sorbitol monoacetal or sorbitol triacetal. , greatly reducing the energy consumption during processing.
- the polymer is Polyethylene or polypropylene.
- the composite catalysts used in the following examples of the invention are mainly as follows:
- Composite catalyst 1 molar ratio of p-toluenesulfonic acid to ethylene glycol monomethyl ether is 3:10
- Composite catalyst 2 molar ratio of p-toluenesulfonic acid to ethylene glycol dimethyl ether is 3:10
- Composite catalyst 3 the molar ratio of benzenesulfonic acid, ethylene glycol dibutyl ether and Sipan-40 is 5:7:10
- the synthesis was carried out in a 2000 L reactor equipped with a thermometer, a stirring paddle, an organic carrier electric heating system and a water-water separator reflux condenser. First, 115 kg of p-chlorobenzaldehyde and 70 kg of solid sorbitol were added to the reaction vessel.
- the synthesis was carried out in a 2000 L reactor equipped with a thermometer, a stirring paddle, an organic carrier electric heating system and a water-water separator reflux condenser. First, 120 kg of p-methylbenzaldehyde and 85 kg of solid sorbitol were added to the reactor.
- the chiller system re-adjust the temperature of the electric heating furnace so that the oil temperature is constant at 100-120 ° C, so that the cyclohexane is continuously circulated and refluxed in the reflux condenser, and the lowest azeotrope formed by the water formed by the condensation reaction of the aldol
- the water is continuously taken out to make the reaction proceed smoothly.
- the water output reaches a predetermined value, the reaction is finished, the crude product is formed, the crude product is transferred to a stainless steel barrel, water is added, and the dispersion is dispersed.
- the chiller system is turned on; the temperature of the electric heating furnace oil is re-adjusted, the oil temperature is kept constant at 100-120 ° C, and the cyclohexane is continuously circulated and refluxed in the reflux condenser, so that the water formed by the aldol condensation reaction is continuously brought.
- the reaction is allowed to proceed smoothly.
- the amount of water reaches a predetermined value, the reaction is completed and the crude product is formed, which takes 1.5 to 2.0 hours.
- the temperature of the electric heating furnace oil is adjusted to 55 ° C. At this time, the solvent cyclohexane is recovered by distillation with residual heat.
- the sample remains large in the system. After the injection, the triacetal is detected in the first blank, and the second blank spectrum is clean. Therefore, a systematic blanking procedure is performed between each sample to remove the residue.
- the sample was analyzed twice and the second analysis data was selected for analysis. The results were automatically calculated by GCMSsolution 4.11SU1 software.
- Injection temperature is 300 ° C
- Injection time is 0.5 minutes
- the oven temperature is 120 ° C
- the total flow rate is 6.0ml/min
- the column flow rate is 3.00ml/min
- the purge flow rate was 3 ml/min, and the temperature program was 120 ° C (1.00 min) to 15 ° C/min to 300 ° C (17.00 min).
- the ion source temperature is 260 ° C
- Interface temperature is 300 ° C
- the acquisition start time is 1.75min
- the acquisition end time is 30.00 min.
- the nucleating agent composition is generally used in PP and PE resin applications in an amount of 1.5 g to 2.5 g (per 1000 g of resin) and an extrusion temperature of 180 to 210 ° C in order to test the nucleating agent composition for PP and PE products.
- the effect, in all of the examples, the nucleating agent composition is added in an amount of from 0.15 to 0.25% (relative to the mass of the PP and PE resin), and the extrusion temperature is from 180 to 210 °C.
- a blank nucleating agent homopolypropylene HP500N resin composition and a blank nucleating agent linear low density polyethylene 7042 resin composition were prepared and granulated in a twin-screw kneading extrusion. , a control sample was obtained.
- the polypropylene composition was injection molded at 230 ° C to prepare a light transmittance, a haze test sample and an impact spline; the polyethylene composition was extruded at 200 ° C to prepare a light transmittance, haze test sample, and molded at 200 ° C. , preparation of impact splines.
- the polypropylene transmittance and haze test sample thickness is 1.0 mm; the polyethylene transmittance and haze test sample thickness is 0.030 mm.
- a transparent nucleating agent containing sorbitol monoacetal and triacetal produces a transparent aspect that is more transparent than a transparent nucleating agent that does not contain sorbitol monoacetal or sorbitol triacetal ( Mainly refers to the excellent performance of light transmittance and haze.
- a transparent nucleating agent containing sorbitol triacetal and sorbitol monoacetal is more transparent than a transparent nucleating agent that does not contain sorbitol triacetal or sorbitol monoacetal (mainly It means excellent in light transmittance and haze.
- the processing temperature that is, the extrusion temperature
- commercially available products commercially available products do not contain sorbitol triacetal or content less than 0.1%, the amount of components contained in the analysis method is the same as above
- the experimental conditions of the product were the same as those of Examples 1-3 and Comparative Examples 1-3.
- the commercially available products have less performance effects on polyethylene and polypropylene than the products of Examples 1-3 of the present invention, and on the other hand, the commercially available products have a relatively high extrusion temperature and a height of about 10-20 °C.
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Abstract
Description
Claims (18)
- 根据权利要求1所述的成核剂组合物,其中R为-Cl、-Br、-CH3或-CH2-CH3。
- 权利要求1或2所述的成核剂组合物的制备方法,该方法包括如下步骤:1)在容器中加入所需加入芳香醛重量的三分之一的芳香醛和所有山梨醇,搅拌形成混合物,2)将环己烷加入到步骤1)的混合物中,3)加入复合催化剂到步骤2)的产物中,4)加热步骤3)的产物至环己烷回流进行醇醛缩合脱水反应,再维持加热0.4-1.0小时5)加入所需加入的芳香醛重量的三分之一的芳香醛和环己烷的混合物到步骤4)的产物中6)加热步骤5)的产物0.4-1.0小时,获得加热混合物,7)加入所需加入的芳香醛重量的三分之一的芳香醛和环己烷的混合物到加热混合物中,维持加热至油水分离器收集的水量摩尔数与山梨醇摩尔数比值为1.5-2.0:1.0,8)降温、减压蒸馏环己烷和水,获得粗产品,9)将获得的粗产品加入水中分散,再加入氢氧化钠和双氧水搅拌,10)压滤,水洗,干燥,粉碎获得白色粉末成核剂组合物。其中芳香醛的结构式如下:其中n为1或2,R选自C1-C8烷基、C1-C4烷氧基、羧基、羟基、氢、卤素和C1-C6烷硫基,复合催化剂为包含对甲苯磺酸和醇醚的混合物。
- 根据权利要求3所述的方法,其中醇醚为乙二醇单甲醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇单丁醚或乙二醇二丁醚,对甲苯磺酸和醇醚的摩尔比为3-5:8-10。
- 根据权利要求3或4所述的方法,其中步骤5)加入的环己烷与步骤1)加入的环己烷的体积比为1:3,步骤7)加入的环己烷与步骤1)加入的环己烷的体积比为1:3,步骤5)和步骤7)加入的环己烷的体积相同。
- 权利要求1或2所述的成核剂组合物用于制备提高性能的聚合物的用途,其中所述聚合物为聚乙烯或聚丙烯,所述性能包括(a)降低的挤出温度,(b)提高的透明性、(c)提高的光泽度、(d)提高的弯曲模量,(e)提高的拉伸强度,(f)提高的制品的热变形温度(g)改进的尺寸稳定性,(h)缩短的成型周期,(i)提高的聚合物产品生产效率中的一种或多种。
- 权利要求1或2的成核剂组合物在制备具有改进透明性和降低挤出温度的聚合物中的用途。
- 一种包含聚合物和权利要求1或2所述成核剂组合物的聚合物组合物,其中成核剂组合物在聚合物组合物中的重量百分比为0.03-0.3%,优选地,成核剂组合物在聚合物组合物中的重量百分比为0.05-0.25%。
- 根据权利要求8所述的聚合物组合物,其中聚合物为聚乙烯或聚丙烯。
- 根据权利要求9所述的聚合物组合物,其中聚乙烯为低密度聚乙烯,中密度聚乙烯、高密度聚乙烯、线形低密度聚乙烯、超高分子量聚乙烯、乙烯共聚物,聚丙烯选自等规聚丙烯,无规聚丙烯、间规聚丙烯、氯化聚丙烯和接枝聚丙烯,优选的,乙烯共聚物为乙烯-丙烯共聚物、EVA、乙烯-丁烯共聚物、乙烯-辛烯共聚物或乙烯不饱和酯共聚物。
- 根据权利要求6或7所述的用途,其中聚合物形态为聚合物膜、聚合物片、聚合物模塑制品或聚合物制品。
- 根据权利要求11所述的用途,其中聚合物的形态为聚合物膜,聚合物片,聚合物模塑制品,改进的性能为提高聚合物膜的、聚合物片的或聚合物模塑制品的弯曲模量和拉伸强度。
- 根据权利要求11所述的用途,其中聚合物形态为聚合物制品,改进的性能为提高聚合物制品的热变形温度和/或改进尺寸稳定性。
- 一种制备具有改进性能的聚合物的方法,该方法包括将权利要求1或2的成核剂组合物加入到不含权利要求1或2的成核剂组合物的聚合物中,以获得改进性能的聚合物,其中所述聚合物为聚乙烯或聚丙烯,相比于未添加成核剂组合物的起始聚合物,所述聚合物具有(a)降低的挤出温度,(b)提高的透明性、(c)提高的光泽度、(d)提高的弯曲模量,(e)提高的拉伸强度,(f)提高的制品的热变形温度(g)改进的尺寸稳定性,(h)缩短的成型周期,(i)提高的聚合物产品生产效率中的至少一种改进的性能。
- 根据权利要求14所述的方法,其中改进的性能为提高的透明性和降低的挤出温度。
- 根据权利要求14所述的方法,其中聚合物形态为聚合物膜、聚合物片、聚合物模塑制品或聚合物制品。
- 根据权利要求16所述的方法,其中聚合物的形态为聚合物膜,聚合物片,聚合物模塑制品,改进的性能为提高聚合物膜的、聚合物片的或聚合物模塑制品的弯曲模量和拉伸强度。
- 根据权利要求16所述的方法,其中聚合物形态为聚合物制品,改进的性能为提高聚合物制品的热变形温度和/或改进尺寸稳定性。
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MYPI2018002766A MY183486A (en) | 2016-09-05 | 2016-09-05 | Nucleator composition comprising sorbitol acetal, sorbitol diacetal and sorbitol triacetal |
EP16909065.1A EP3498713B1 (en) | 2016-09-05 | 2016-09-05 | Transparent nucleating agent composition comprising sorbitol triacetals and monoacetals |
BR112019000438-6A BR112019000438B1 (pt) | 2016-09-05 | 2016-09-05 | Composição do nucleador compreendendo acetato de sorbitol, diacetato de sorbitol e tiracetal de sorbitol, seu uso, método para a preparação da mesma, composição de polímero e método de preparação de um polímero aperfeiçoado |
CN201680000856.6A CN106795326B (zh) | 2016-09-05 | 2016-09-05 | 一种包含山梨醇三缩醛和单缩醛的透明成核剂组合物 |
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US15/542,818 US10208057B2 (en) | 2016-09-05 | 2016-09-05 | Nucleator composition comprising sorbitol acetal, sorbitol diacetal and sorbitol triacetal |
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