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 PDF

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WO2018040093A1
WO2018040093A1 PCT/CN2016/098059 CN2016098059W WO2018040093A1 WO 2018040093 A1 WO2018040093 A1 WO 2018040093A1 CN 2016098059 W CN2016098059 W CN 2016098059W WO 2018040093 A1 WO2018040093 A1 WO 2018040093A1
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polymer
nucleating agent
formula
agent composition
cyclohexane
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PCT/CN2016/098059
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English (en)
French (fr)
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赵文林
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呈和科技股份有限公司
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Priority to BR112019000438-6A priority Critical patent/BR112019000438B1/pt
Priority to RU2019102663A priority patent/RU2729657C2/ru
Priority to JP2019520183A priority patent/JP6672528B2/ja
Priority to MYPI2018002766A priority patent/MY183486A/en
Priority to EP16909065.1A priority patent/EP3498713B1/en
Application filed by 呈和科技股份有限公司 filed Critical 呈和科技股份有限公司
Priority to CN201680000856.6A priority patent/CN106795326B/zh
Priority to KR1020187036703A priority patent/KR102634775B1/ko
Priority to US15/542,818 priority patent/US10208057B2/en
Priority to PCT/CN2016/098059 priority patent/WO2018040093A1/zh
Publication of WO2018040093A1 publication Critical patent/WO2018040093A1/zh
Priority to SA519401201A priority patent/SA519401201B1/ar

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    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

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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  • Organic Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

一种包含山梨醇三缩醛的成核剂组合物，该成核剂组合物包含山梨醇二缩醛、山梨醇三缩醛和山梨醇单缩醛，该组合物改善了对聚合物成核的性能，提高了聚合物薄膜、片材及模塑等制品的透明性、光泽度、弯曲模量及拉伸强度，改善制品的热变形温度和尺寸稳定性。

Description

一种包含山梨醇三缩醛和单缩醛的透明成核剂组合物 技术领域
本发明涉及制备聚合物的成核剂及其成核剂的用途，特别是涉及包含山梨醇三缩醛，山梨醇二缩醛和单缩醛的成核剂组合物及其制备方法。
背景技术
目前在工业上所用的山梨醇类成核剂基本上是以二缩醛为基本成分，将三缩醛产物和单缩醛作为杂质从产品中分离出去，或者在制备过程中控制反应条件使其不产生三缩醛和单缩醛。例如中国专利申请号为CN200410026622.8所公开的将成核剂进行纯化，除去其中单亚甲基亚苄基山梨糖醇和三亚甲基亚苄基山梨糖醇，使得产品的纯度提高，但是专利CN200410026622.8中，对于处理后的产品的纯度无法达到100％，无法确定其中的杂质为何物，及其杂质的含量为多少。
还有的山梨醇类成核剂中包含的三缩醛的含量可能过高，或者三缩醛的含量可能没有，例如中国专利申请号CN200810219978.1中公开的成核剂制备方法，其在制备中控制了芳香醛的加入量，并控制反应时间和温度，由于反应过程并没有仔细控制加料顺序和加料的量，使得反应产物中的二缩醛和三缩醛的产物无法控制，不清楚其中产物的准确含量范围，而且也没有发现含有特定含量的三缩醛的成核剂对于产品的性能的作用。
发明内容
本发明为解决上述技术问题，本发明提出了一种能够含有与山梨醇二缩醛成特定比例的山梨醇三缩醛和单缩醛的成核剂组合物，该组合物实现了在聚合物成核过程中起到的特殊的作用。而且确定了含有不同浓度山梨醇三缩醛和单缩醛的成核剂在不同聚合物成核过程的特定作用。
本发明中，成核剂是指成核的制剂，其用于聚合物的成核。
第一个方面，本发明提供了一种成核剂组合物，该组合物包含如下式(I)的化合物、式(II)的化合物、式(III)化合物和式(IV)化合物：
Figure PCTCN2016098059-appb-000001
式(I)、式(II)、式(III)和式(IV)中的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，该组合物中，式(I)化合物重量、式(II)化合物重量与式(III)和式(IV)化合物重量之和的重量之比为：(97.00-99.90)：(0.20-8.00)：(0.02-1.00)。
优选的，式(I)化合物重量、式(II)化合物重量与式(III)和式(IV)化合物重量之和的重量之比为：(97.00-99.90)：(0.20-5.00)：(0.02-0.80)。
优选的，式(I)化合物重量、式(II)化合物重量与式(III)和式(IV)化合物重量之和的重量之比为：(97.00-99.90)：(0.20-3.00)：(0.02-0.15)。
上述组合物中，优选的，R为-Cl、-Br、-CH3或-CH2-CH3。
更为具体的，本发明提供了一种组合物，该组合物由上述式(I)化合物、式(II)化合物、式(III)化合物和式(IV)化合物组成。
优选的，在本发明中，式(I)代表的化合物简称为山梨醇双缩醛，式(II)代表的化合物简称为山梨醇三缩醛，式(III)和式(IV)代表的化合物简称为山梨醇单缩醛。
第二方面，本发明提供了一种上述成核剂组合物的制备方法，该制备方法包括如下步骤：
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。
上述方法中，所述的芳香醛为如下结构式：
Figure PCTCN2016098059-appb-000002
其中n为1或2，和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。
其中，复合催化剂为包含对甲苯磺酸和醇醚的混合物。
优选的，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，并且，步骤5)和步骤7)加入的环己烷的体积相同。
优选的，芳香醛为对氯苯甲醛、对溴苯甲醛、对甲基苯甲醛、对乙基苯甲醛，3,4二甲基苯甲醛，3,4二乙基苯甲醛，3,4二氯苯甲醛或3,4二溴苯甲醛。
优选的，酸醚复合催化剂为包含对甲苯磺酸和醇醚的混合物，醇醚为乙二醇的醚，优选为乙二醇单甲醚、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，特别优选醇醚为乙二醇甲醚。混合物中，对甲苯磺酸和醇醚的摩尔比为3-5:8-10。
第三方面，本发明还提供了上述制备的成核剂组合物用于制备具有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，所述性能包括降低挤出温度，提高聚合物膜、聚合物片及聚合物模塑制品的透明性、光泽度、弯曲模量和/或拉伸强度，提高聚合物制品的热变形温度和/或尺寸稳定性、缩短聚合物制品成型周期和提高聚合物制品的生产效率中的一种或多种。
可选择的，本发明提供了上述制备的成核剂组合物用于制备具有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，提高的性能包括(a)降低挤出温度，(b)提高透明性、(c)提高光泽度、(d)提高弯曲模量，(e)提高拉伸强度，(f)提高热变形温度(g)提高尺寸稳定性，(h)缩短成型周期，(i)提高聚合物产品生产效率中的一种或多种。
优选地，本发明提供了上述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。
上述用途中，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。
本发明还提供了制备具有改进性能的聚合物的方法，该方法包括将上述成核剂组合物加入到聚合物中的步骤。其中所述聚合物为聚乙烯或聚丙烯，所述性能为降低挤出温度，提高聚合物膜、聚合物片及聚合物模塑制品的透明性、光泽度、弯曲模量和/或拉伸强度，提高聚合物制品的热变形温度和/或尺寸稳定性、缩短聚合物制品成型周期和提高聚合物产品的生产效率中的一种或多种。
本发明还提供了制备具有改进性能的聚合物的方法，该方法包括将上述成核剂组合物加入到不含本发明上述成核剂组合物的聚合物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，相比于未添加本发明的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性能。
优选地，在上述方法中，提高的性能为提高的透明性和/或降低的挤出温度。
优选的，上述方法中，提高性能的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。具体的，改进性能的聚合物的形态为聚合物膜，聚合物片，聚合物模塑制品时，则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。优选的，改进的聚合物形态为聚合物制品时，改进的性能为提高的热变形温度和/或提高的尺寸稳定性。
本发明还提供了制备具有改进透明度和降低挤出温度的聚合物的方法，包括将本发明上述透明成核剂组合物加入到聚合物中的步骤。
优选的，聚合物为聚乙烯或聚丙烯。
第四个方面，本发明提供了一种包含聚合物和上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％。优选的，所述聚合物为聚乙烯或聚丙烯。
本发明所述的聚乙烯包括但不限于低密度聚乙烯，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。其中乙烯共聚物包括但不限于乙烯-丙烯共聚物、EVA、乙烯-丁烯共聚物、乙烯-辛烯共聚物、乙烯不饱和酯共聚物等。
本发明所述的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等。
本发明的上述成核剂组合物对于PE(聚乙烯)和PP(聚丙烯)的某些性能具有特别的提高，尤其是能够降低PE和PP的加工温度，含有山梨醇三缩醛和山梨醇单缩醛的成核剂相对于纯的山梨醇双缩醛，或者是不含有山梨醇单缩醛，或不含有山梨醇三缩醛的透明成核剂来说，挤出温度降低10℃以上，大大降低了加工过程中的能耗。而且在改善其性能方面具有预料不到的效果，例如：提高聚合物薄膜、片材及模塑等制品的透明性、光泽度、弯曲模量及拉伸强度，提高制品的热变形温度和尺寸稳定性，缩短成型周期，提高生产效率，所述聚合物为 聚乙烯或聚丙烯。
具体实施方式
本发明下面的实施例中所用的复合催化剂主要有以下几种：
复合催化剂1：对甲苯磺酸与乙二醇单甲醚的摩尔比为3:10
复合催化剂2：对甲苯磺酸与乙二醇二甲醚的摩尔比为3:10
复合催化剂3：苯磺酸、乙二醇二丁醚和斯盘-40的摩尔比为5:7:10
实施例1 成核剂组合物1
在2000L反应釜中加入85kg的固体山梨醇和45公斤的对氯苯甲醛，再加入约600L的环己烷，开动搅拌30分钟；并加入10公斤的复合催化剂1，加热搅拌至溶剂环己烷回流，维持反应半小时后再加入45公斤对氯苯甲醛和200L环己烷的混合物，再维持反应半小时后加入45公斤的对氯苯甲醛和200L环己烷的混合物，继续反应2.3小时，在油水分离器中收集缩合反应脱水约14升时，开始回收环己烷，然后降温、减压蒸馏回收剩余的环己烷和水，在获得产品加入水进行分散，加入3kg的氢氧化钠搅拌，再加入20kg浓度约为30％wt的双氧水搅拌，然后水洗，压滤，干燥，获得白色粉末产品1，用气相色谱-质谱联用仪分析，其中双(对氯苄叉)山梨醇190.5kg，三(对氯苄叉)山梨醇5.69kg，单(对氯苄叉)山梨醇0.04kg，(重量比约为97.155:2.902:0.0204)。
实施例2 成核剂组合物2
在2000L反应釜中加入85kg的固体山梨醇和38.6公斤的对甲基苯甲醛，再加入约600L的环己烷，开动搅拌30分钟；并加入10公斤的复合催化剂2，加热搅拌至溶剂环己烷回流，维持反应半小时后再加入38.6公斤对氯苯甲醛和200L环己烷的混合物，再维持反应半小时后加入38.6公斤的对氯苯甲醛和200L环己烷的混合物，继续反应2.4小时，在油水分离器中收集缩合反应脱水约15升时，开始回收环己烷，然后降温、减压蒸馏回收剩余的环己烷和水，在获得产品加入水进行分散，加入3kg的氢氧化钠搅拌，再加入20kg浓度约为30％的双氧水搅拌，然后水洗，压滤，干燥，获得白色粉末产品2，用气相色谱-质谱联用仪分析，其中双(对甲基苄叉)山梨醇173.2kg，三(对甲基苄叉)山梨醇0.35kg，单(对甲基苄叉)山梨醇1.384kg，(重量比约为98.90:0.230:0.790)。
实施例3 成核剂组合物3
在1000L反应釜中加入37kg的3,4-二甲基苯甲醛和75kg的固体山梨醇，再加入250L的溶剂环己烷，开启反应釜搅拌器，再打开电加热炉加热，维持油温65℃，然后再慢慢加入9.6kg复合催化剂3，此过程所需时间约为10分钟。加完后，开启冷水机系统；重新调节电加热炉油温，使油温恒定在100～120℃，维持半小时后再加入37kg的3,4-二甲基苯甲醛和125L的溶剂环己烷，维持半小时后，再加入37kg的3,4-二甲基苯甲醛和125L的溶剂环己烷，使环己烷在回流冷凝器不断地循环回流，将醇醛缩合反应生成的水不断地带出，使反应顺利进行，当出水量达到14.8升时，开始回收环已烷，然后降温减压蒸馏回收剩余的环己烷和水，在获得产品加入水进行分散，加入3kg的氢氧化钠搅拌，再加入20kg浓度约为30％的双氧水搅拌，然后水洗，压滤，干燥，获得白色粉末产品3，用气相色谱-质谱联用仪分析，其中双(3,4-二甲基苄叉)山梨醇169.1kg，三(3,4-二甲基苄叉)山梨醇1.029kg，单(3,4-二甲基苄叉)山梨醇0.345，(重量比约为99.177:0.604:0.148)。
对比例1 对比成核剂组合物1
在配有测温仪、搅拌桨、有机载体电加热系统和具有油水分离器回流冷凝器的2000L反应釜中进行合成，首先在反应釜中加入115kg的对氯苯甲醛和70kg的固体山梨醇，再加入约600L的溶剂环己烷，上紧手孔盖；开启反应釜搅拌马达进行搅拌，再打开电加热炉加热，维持油温55℃，使原料充分混合，约需30分钟；经确认对氯苯甲醛全溶解后，再慢慢加入苯磺酸/乙二醇甲醚复合催化剂，其用量为苯磺酸3.5kg/乙二醇甲醚3.6kg，约10分钟加完后，开启冷水机系统；重新调节电加热炉油温，使油温恒定在100～120℃，使环己烷在回流冷凝器不断地循环回流，它和醇醛缩合反应生成的水形成的最低共沸混合物经回流冷凝器油水分离后不断地将水带出，使反应顺利进行，当出水量达到预定值时，反应结束，粗产品生成，将粗产品转移到不锈钢桶中，加水，经分散机分散后再过胶体磨，然后在离心机内淋洗、脱水；经脱水的粗产品再转入不锈钢桶中，加入4kg NaOH，高速搅拌至浆化后再加入35kg H2O2(H2O2浓度约为30％)，搅拌4小时，然后再水洗，离心脱水，重复两次；干燥，打粉，得到对比产品1。用气相色谱-质谱联用仪分析，不含有单(对氯苄叉)山梨醇。
对比例2 对比成核剂组合物2
在配有测温仪、搅拌桨、有机载体电加热系统和具有油水分离器回流冷凝器的2000L反应釜中进行合成，首先在反应釜中加入120kg的对甲基苯甲醛和85kg的固体山梨醇，再加入约600L的溶剂环己烷，上紧手孔盖；开启反应釜搅拌马达进行搅拌，再打开电加热炉加热，维持油温55℃，使原料充分混合，约需30分钟；经确认对甲基苯甲醛全溶解后，再慢慢加入苯磺酸/乙二醇甲醚复合催化剂，其用量为苯磺酸3.5kg/乙二醇甲醚3.6kg，约10分钟加完后，开启冷水机系统；重新调节电加热炉油温，使油温恒定在100～120℃，使环己烷在回流冷凝器不断地循环回流，它和醇醛缩合反应生成的水形成的最低共沸混合物经回流冷凝器油水分离后不断地将水带出，使反应顺利进行，当出水量达到预定值时，反应结束，粗产品生成，将粗产品转移到不锈钢桶中，加水，经分散机分散后再过胶体磨，然后在离心机内淋洗、脱水；经脱水的粗产品再转入不锈钢桶中，加入4kg NaOH，高速搅拌至浆化后再加入35kg H2O2(H2O2浓度约为30％，搅拌4小时，然后再水洗，离心脱水，重复两次；干燥，打粉，得到对比产品2。用气相色谱-质谱联用仪分析，不含有三(对甲基苄叉)山梨醇。
对比例3 对比成核剂组合物3
化学合成在配有测温仪、搅拌桨、有机载体电加热系统和具有油水分离器回流冷凝器的1000L反应釜中进行合成，首先在反应釜中加入108kg的3,4-二甲基苯甲醛和73kg的固体山梨醇，再加入约450L的溶剂环己烷，开启反应釜搅拌器，维持油温55℃，使3,4-二甲基苯甲醛和固体山梨醇混合，再慢慢加入对甲苯磺酸/乙二醇单甲醚/斯盘-60构成的复合催化剂8.3kg，此过程所需时间约为10分钟。加完后，开启冷水机系统；重新调节电加热炉油温，使油温恒定在100～120℃，使环己烷在回流冷凝器不断地循环回流，使醇醛缩合反应生成的水不断地带出，使反应顺利进行，当出水量达到预定值时，反应结束，粗产品生成，耗时1.5-2.0小时。溶剂回收合成反应结束后，将电加热炉油温调至55℃，此时利用余热开始蒸馏回收溶剂环己烷，当溶剂馏出量减少时，开启真空系统，适当减压直至环己烷蒸尽为止，反应釜中留下得对比产品3。用气相色谱-质谱联用仪分析，不含有单(3,4-二甲基苄叉)山梨醇
气相色谱-质谱联用仪分析测量实施例1-3和对比例1-3的产品的方法为：
称取约0.5000g的实施例产品于10.0ml容量瓶，
用二甲基亚砜超声溶液定容；
通过GCMS面积归一化法进行全组分测定，色谱图不对原料杂质(3,4-二甲基苯甲醛)进行积分比较；
经过实验分析知样品在系统中残留较大，进样后在第一次空白检出三缩醛，第二次空白谱图干净，故每个样品间进行一次系统空白程序以除去残留，每个样品进行两次分析，选取第二次分析数据进行解析。测定结果由GCMSsolution 4.11SU1软件自动计算得出。
气相色谱的条件为：
进样温度300℃，
进样时间0.5分钟，
柱箱温度120℃，
压力91.0kPa，
总流量6.0ml/min，
柱流量3.00ml/min，
线速度65.0cm/sec，
吹扫流量3ml/min，升温程序：120℃(1.00min)～15℃/min～300℃(17.00min)。
质谱的条件为：
离子源温度260℃,
接口温度300℃,
扫描速度2000,
扫描范围m/z80～m/z1000,
溶剂延迟时1.50min,
采集开始时间1.75min,
采集结束时间30.00min。
实验实施例
测试实施例1-3的成核剂对PP(聚丙烯)和PE(聚乙烯)的性能影响
分别向聚乙烯和聚丙烯中加入实施例1-3获得的成核剂组合物白色粉末状产品1-3以及对比例的对比产品1-3，测量对聚合物的影响：
成核剂组合物在PP和PE树脂应用中，添加量一般为1.5g～2.5g(每1000g树脂)，挤出温度为180～210℃，为了测试成核剂组合物对PP和PE制品产生的影响，在所有实施例中，成核剂组合物添加量为0.15～0.25％(相对于PP和PE树脂的质量)，挤出温度为180～210℃。
将2g的实施例1-10的成核剂组合物和对比例的产品按添加量分别加入到1000g的树脂中，在高速混合机中混合5分钟后，成为树脂混合物，在双螺杆混炼挤出造粒。挤出温度为180～210℃，获得样品。
同样地，按照上述试验样品的制备方法，制备空白成核剂的均聚聚丙烯HP500N树脂组合物和空白成核剂的线性低密度聚乙烯7042树脂组合物，在双螺杆混炼挤出造粒，获得对照样品。
将聚丙烯组合物在230℃注塑，制备透光率、雾度测试样和冲击样条；聚乙烯组合物在200℃挤出吹膜，制备透光率、雾度测试样，在200℃注塑，制备冲击样条。其中聚丙烯透光率、雾度测试样厚度为1.0mm；聚乙烯透光率、雾度测试样厚度为0.030mm。
下面的表列出了实施例制备的成核剂对于聚乙烯和聚丙烯性能的影响以及对其加工温度的影响。
表1实施例成核剂对注塑圆片的性能影响(成核剂加入量为聚合物的0.2％wt)
Figure PCTCN2016098059-appb-000003
从上面的实验结果能够看出，本发明的实施例1-3的产品用于制备聚烯烃产 品后，改善了聚合物的透明性。
对于聚乙烯来说，含有山梨醇单缩醛和三缩醛的透明成核剂产生的透明方面的性能比不含山梨醇单缩醛或山梨醇三缩醛的透明成核剂的透明方面(主要是指透光率和雾度)的性能优异。
对于聚丙烯来说，含有山梨醇三缩醛和山梨醇单缩醛的透明成核剂来说，比不含有山梨醇三缩醛或山梨醇单缩醛透明成核剂产生的透明方面(主要是指透光率和雾度)的性能优异。
对于加工温度，也就是挤出温度来说，通过与市购产品进行对比(市购产品中不含山梨醇三缩醛或含量低于0.1％，所含成分的量分析方法同上)，市购产品的实验条件与实施例1-3和对照例1-3的实验条件相同。一方面市购产品对聚乙烯和聚丙烯的性能效果不如本发明的实施例1-3的产品，另一方面市购产品挤出温度比较高，高约10-20℃。
表2市购产品成核剂对注塑圆片的性能影响(成核剂加入量为聚合物的0.2％wt)
Figure PCTCN2016098059-appb-000004
表2中市购产品中不含有山梨醇三缩醛，采购自中国市场。

Claims (18)

  1. 一种成核剂组合物，该组合物包含如下式(I)的化合物、式(II)的化合物、式(III)化合物和式(IV)化合物：
    Figure PCTCN2016098059-appb-100001
    式(I)、式(II)、式(III)和式(IV)中的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，式(I)化合物重量、式(II)化合物重量与式(III)和式(IV)化合物重量之和的重量之比为：(97.00-99.90)：(0.20-8.00)：(0.02-1.00)。
  2. 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。
  3. 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：
    Figure PCTCN2016098059-appb-100002
    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。
  4. 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。
  5. 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。
  6. 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。
  7. 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。
  8. 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％。
  9. 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。
  10. 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。
  11. 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。
  12. 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。
  13. 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。
  14. 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。
  15. 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。
  16. 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。
  17. 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。
  18. 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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