WO2016127353A1 - Hydrogenated styrene thermoplastic elastomer and preparation method therefor - Google Patents

Abstract

The present invention provides a hydrogenated styrene thermoplastic elastomer with a unique micro-phase structure and a preparation method therefor. The styrene monomers in a block copolymer have a weight percentage content of 50-80%, and a number-average molecular weight of 50000-300000 g/mol. A micro-phase separation structure in the hydrogenated styrene thermoplastic elastomer with the unique micro-phase structure is very distinctive, and polystyrene exists in a dispersion phase form in a polymer matrix; however, not only does a polystyrene dispersion phase with an average particle size of 400-900 nm exist, but also a polystyrene dispersion phase with the average particle size of 10-95 nm exists. The thermoplastic elastomer has an obvious internal friction peak (tanδ) at -30-50 °C, a peak value of the internal friction peak is -5-10 °C, and the peak value tanδ ≥ 0.3. The thermoplastic elastomer has an optimum fogging effect when being used for producing products such as thin films, wires, sheets and the like; and moreover, the fogging effect is very exquisite, and the hand feeling is dry and comfortable.

Description

一种氢化苯乙烯类热塑性弹性体及其制备方法Hydrogenated styrene thermoplastic elastomer and preparation method thereof 技术领域Technical field

本发明涉及一种具有特殊微相结构的氢化苯乙烯类热塑性弹性体及其制备方法，属于聚合物材料制备领域。The invention relates to a hydrogenated styrene-based thermoplastic elastomer having a special micro-phase structure and a preparation method thereof, and belongs to the field of preparation of polymer materials.

背景技术Background technique

苯乙烯类热塑性弹性体是苯乙烯-共轭二烯类共聚物及其衍生物的统称。苯乙烯-共轭二烯类共聚物中的嵌段共聚物(包括两嵌段和三嵌段)具有热塑性弹性体性质，是最早和最广泛研究的品种。其中产量最大的有三种：聚苯乙烯-聚丁二烯-聚苯乙烯三嵌段共聚物(SBS)，聚苯乙烯-聚异戊二烯-聚苯乙烯三嵌段共聚物(SIS)和聚苯乙烯-氢化聚丁二烯-聚苯乙烯三嵌段共聚物(SEBS)。The styrenic thermoplastic elastomer is a general term for styrene-conjugated diene-based copolymers and derivatives thereof. The block copolymers (including diblocks and triblocks) in styrene-conjugated diene-based copolymers have thermoplastic elastomer properties and are the earliest and most widely studied varieties. Three of the largest yields are: polystyrene-polybutadiene-polystyrene triblock copolymer (SBS), polystyrene-polyisoprene-polystyrene triblock copolymer (SIS), and Polystyrene-hydrogenated polybutadiene-polystyrene triblock copolymer (SEBS).

SBS和SIS是研究的最早的产品，早在20世纪60年代Phillips石油公司和Shell化学公司就对其实现了工业化生产。但是却发现SBS的耐老化性和化学稳定性并不好。因此，Shell化学公司(现Kraton)的研究人员将SBS的软段进行了高度氢化，得到了力学性能更好，化学稳定性更优异的热塑性弹性体SEBS。Shell化学公司在20世纪70年代也对其进行了工业化生产。目前，全世界SBS，SIS和SEBS的年总产量已超过200万吨，在各个领域都有着广泛的应用。SBS and SIS were the earliest products of research, and industrialized production was achieved by Phillips Petroleum and Shell Chemical in the 1960s. However, it was found that the aging resistance and chemical stability of SBS were not good. Therefore, researchers at Shell Chemical Company (now Kraton) have highly hydrogenated the soft segment of SBS to obtain a thermoplastic elastomer SEBS with better mechanical properties and better chemical stability. Shell Chemical also industrialized it in the 1970s. At present, the annual total output of SBS, SIS and SEBS in the world has exceeded 2 million tons, and it has been widely used in various fields.

在商业化的SEBS中一般聚苯乙烯嵌段为分散相，而弹性体嵌段为连续相。正是因为这种微相分离结构，在常温下聚苯乙烯嵌段硬而强，并将弹性嵌段锁接成物理交联的网络，使其拥有了弹性体的性质。而当温度升高，聚苯乙烯开始流动时，其又可以像塑料一样进行反复加工。这使得SEBS具有了塑料和橡胶的双重性质，特别是赋予了SEBS与传统硫化橡胶相似的弹性。In commercial SEBS, the polystyrene block is generally the dispersed phase and the elastomer block is the continuous phase. Because of this microphase-separated structure, the polystyrene block is hard and strong at normal temperature, and the elastic block is locked into a physically crosslinked network, giving it the properties of an elastomer. When the temperature rises and the polystyrene begins to flow, it can be processed repeatedly like plastic. This gives SEBS a dual nature of plastics and rubber, in particular giving SEBS a similar elasticity to conventional vulcanized rubber.

在现有技术中，为了得到雾面效果的聚合物线材和片材等产品，一般是采用将聚合物与其它一定量添加剂(如无机填料等)相配合，或与其它一定量不相容共聚物(如PA、PC)共混，或者直接对聚合物进行动态硫 化等手段，但这些手段能够取得的效果有限。对于苯乙烯类热塑性弹性体，在有些情况下，当添加剂的量特别大时(如无机填料SiO₂的量达到60-70％)、其它共聚物的量特别大时(如PA、PC的量达到50-60％)、或者深度动态硫化后，也可以得到有限的雾面效果，但此时苯乙烯类热塑性弹性体已基本失去了热塑性弹性体的性质，且其它各种性能，特别是弹性，硬度，流动性，强度等也均有本质改变。In the prior art, in order to obtain a matte-effect polymer wire and sheet, etc., the polymer is generally blended with other certain amounts of additives (such as inorganic fillers), or with other amounts of incompatible copolymerization. The blending of materials (such as PA, PC), or direct vulcanization of the polymer, but these methods can achieve limited results. For styrenic thermoplastic elastomers, in some cases, when the amount of additives is particularly large (for example, the amount of inorganic filler SiO ₂ reaches 60-70%), and the amount of other copolymers is particularly large (such as the amount of PA, PC) After achieving 50-60%) or deep dynamic vulcanization, a limited matte effect can also be obtained, but at this time the styrenic thermoplastic elastomer has substantially lost the properties of the thermoplastic elastomer, and various other properties, especially elasticity. , hardness, fluidity, strength, etc. also have essential changes.

本发明公开了一种采用新技术手段制备的具备亚光或磨砂效果的氢化苯乙烯类热塑性弹性体，其具有较高的苯乙烯单体单元含量，并且表现出良好的动态机械性能、粘弹性和减震性，以及良好的亚光或磨砂效果。The invention discloses a hydrogenated styrene-based thermoplastic elastomer prepared by a new technology and having a matt or matte effect, which has a high content of styrene monomer units and exhibits good dynamic mechanical properties and viscoelasticity. And shock absorption, as well as good matt or matte finish.

发明内容Summary of the invention

为了解决上述问题，本发明的发明人发现，通过控制聚合条件，可以有效地得到苯乙烯单体单元含量高并且具备良好的亚光或磨砂效果的氢化苯乙烯类热塑性弹性体。令人惊讶地，本申请的发明人还发现，当该弹性体中嵌段共聚物组分中苯乙烯类单体的总质量含量达到40-80％时，仍表现出典型热塑性弹性体的性质，这完全与传统常识相悖。In order to solve the above problems, the inventors of the present invention have found that by controlling the polymerization conditions, a hydrogenated styrene-based thermoplastic elastomer having a high content of a styrene monomer unit and having a good matt or matte effect can be obtained efficiently. Surprisingly, the inventors of the present application have also discovered that when the total mass content of the styrenic monomer in the block copolymer component of the elastomer reaches 40-80%, the properties of a typical thermoplastic elastomer are still exhibited. This is completely contrary to traditional common sense.

另外，本发明在同一个聚合釜中得到了单分散无规聚苯乙烯和苯乙烯类-丁二烯类嵌段共聚物，经氢化后获得了具有特殊的微相分离结构的氢化苯乙烯类热塑性弹性体，其具有亚光和雾面的表面效果，且雾面的效果十分细腻，特别适用于制造高端雾面效果的薄膜、线材和片材等产品。In addition, the present invention obtains a monodisperse atactic polystyrene and a styrene-butadiene block copolymer in the same polymerization vessel, and obtains a hydrogenated styrene having a special microphase separation structure after hydrogenation. It is a thermoplastic elastomer with a matt and matte surface effect, and the matte effect is very fine, especially suitable for the production of high-end matte film, wire and sheet.

因此，本发明的一个方面提供氢化苯乙烯类热塑性弹性体，基于热塑性弹性体的总重量计，包含以下组分：Accordingly, one aspect of the present invention provides a hydrogenated styrene-based thermoplastic elastomer comprising the following components based on the total weight of the thermoplastic elastomer:

1)55-92％的氢化苯乙烯类-丁二烯类嵌段共聚物，其具有如下结构式：1) 55-92% of a hydrogenated styrene-butadiene block copolymer having the following structural formula:

S¹ _p-D-S² _q  (I)S ¹ _p -DS ² _q (I)

其中：among them:

S¹和S²独立地为苯乙烯类单体聚合嵌段，S¹和S²重量分别占所述嵌段共聚物总重量的8.0-20.0％； S ¹ and S ^{2 are} independently a styrene monomer polymer block, and the weights of S ¹ and S ² are respectively 8.0 to 20.0% by weight of the total weight of the block copolymer;

D为苯乙烯类单体与氢化共轭二烯类单体的共聚嵌段；D is a copolymer block of a styrene monomer and a hydrogenated conjugated diene monomer;

p和q各自独立地为0或1，但不能同时为0；p and q are each independently 0 or 1, but not simultaneously 0;

S¹、S²和D中的苯乙烯类单体单元可以相同或不同；The styrenic monomer units in S ¹ , S ² and D may be the same or different;

其中苯乙烯类单体单元为所述氢化苯乙烯-共轭二烯类嵌段共聚物总重量的50-80重量％；Wherein the styrene monomer unit is 50 to 80% by weight based on the total weight of the hydrogenated styrene-conjugated diene block copolymer;

2)8-45％的单分散无规聚苯乙烯。2) 8-45% monodisperse atactic polystyrene.

本发明的另一个方面提供了一种氢化苯乙烯类热塑性弹性体的制备方法，其包括以下步骤：Another aspect of the present invention provides a method of producing a hydrogenated styrene-based thermoplastic elastomer comprising the steps of:

(i)第一段聚合：使苯乙烯类单体在聚合釜中进行阴离子活性聚合，待单体转化率至少达到95％时，苯乙烯类单体活性种的30-65重量％被部分灭活得到所述组分2)，在该聚合釜中继续加入苯乙烯类单体使得未灭活部分进行聚合或直接进行第二段聚合；(i) First-stage polymerization: anionic living polymerization is carried out in a polymerization vessel in a styrene monomer. When the monomer conversion rate is at least 95%, 30-65% by weight of the styrene monomer active species is partially eliminated. The component 2) is obtained by living, and the styrene monomer is continuously added in the polymerization vessel so that the non-inactivated portion is polymerized or directly subjected to the second-stage polymerization;

(ii)第二段聚合：待单体转化率至少达到95％时，向聚合釜中至少分3批加入共轭二烯烃与苯乙烯类单体的混合物进行所述第二段聚合，其中后一批次在前一批次的转化率至少达到95％时加入，每一批次的共轭二烯烃与苯乙烯类单体可以彼此相同或不同；(ii) second stage polymerization: when the monomer conversion rate is at least 95%, the second stage polymerization is carried out by adding a mixture of a conjugated diene and a styrene monomer to the polymerization tank in at least three batches, wherein One batch is added when the conversion rate of the previous batch is at least 95%, and each batch of the conjugated diene and the styrene monomer may be the same or different from each other;

(iii)任选的第三段聚合：向聚合釜中加入苯乙烯类单体进行第三段聚合；(iii) optional third stage polymerization: adding a styrenic monomer to the polymerization vessel for the third stage polymerization;

(iv)熟化：待第二段聚合或者在存在第三段聚合时待第三段聚合中单体转化率至少达到95％后，继续在反应釜内熟化，得到线型聚合物；(iv) aging: after the second stage polymerization or in the presence of the third stage polymerization, after the monomer conversion rate in the third stage polymerization reaches at least 95%, the aging is continued in the reactor to obtain a linear polymer;

(v)任选的偶联：向聚合釜中加入偶联剂使反应产物偶联，获得星型聚合物；(v) optional coupling: a coupling agent is added to the polymerization vessel to couple the reaction product to obtain a star polymer;

将步骤(iv)或(v)中得到的聚苯乙烯胶液转入氢化釜、灭活，并在加氢催化剂存在下对混合物进行氢化。The polystyrene gum obtained in step (iv) or (v) is transferred to a hydrogenation vessel, inactivated, and the mixture is hydrogenated in the presence of a hydrogenation catalyst.

具体实施方式detailed description

本发明中，除非特别指明，术语“微嵌段”是指每个共聚嵌段中由相同单体单元构成的结构部分。 In the present invention, the term "microblock" means a structural moiety composed of the same monomer unit in each copolymer block unless otherwise specified.

本文中使用的术语“微相结构”是指通过显微镜观察可以界定出的平均直径为10nm以上的相的微观结构形态。The term "microphase structure" as used herein refers to a microstructure morphology of a phase having an average diameter of 10 nm or more which can be defined by microscopic observation.

本发明提供了一种具有特殊微相结构的氢化苯乙烯类热塑性弹性体。通过显微镜观察，在本发明的氢化苯乙烯类热塑性弹性体中，聚苯乙烯以分散相形式存在于聚合物基体中，并且存在平均粒径为400-900nm大的聚苯乙烯分散相以及平均粒径为10-95nm小的聚苯乙烯分散相。The present invention provides a hydrogenated styrene-based thermoplastic elastomer having a special microphase structure. In the hydrogenated styrene-based thermoplastic elastomer of the present invention, polystyrene is present in a polymer matrix in the form of a dispersed phase, and a polystyrene dispersed phase having an average particle diameter of 400 to 900 nm and an average particle are observed by a microscope. A polystyrene dispersed phase having a diameter of 10 to 95 nm.

本发明的氢化苯乙烯类热塑性弹性体包含以下组分，均基于热塑性弹性体的总重量计：The hydrogenated styrenic thermoplastic elastomer of the present invention comprises the following components, each based on the total weight of the thermoplastic elastomer:

1)55-92％的氢化苯乙烯类-丁二烯类嵌段共聚物，其具有如下结构式：1) 55-92% of a hydrogenated styrene-butadiene block copolymer having the following structural formula:

S¹ _p-D-S² _q  (I)S ¹ _p -DS ² _q (I)

其中：among them:

S¹和S²独立地为苯乙烯类单体聚合嵌段，S¹和S²重量分别占所述嵌段共聚物总重量的8.0-20.0％；S ¹ and S ^{2 are} independently a styrene monomer polymer block, and the weights of S ¹ and S ² are respectively 8.0 to 20.0% by weight of the total weight of the block copolymer;

D为苯乙烯类单体与共轭二烯类单体的共聚嵌段；D is a copolymerized block of a styrene monomer and a conjugated diene monomer;

p和q各自独立地为0或1，但不能同时为0；p and q are each independently 0 or 1, but not simultaneously 0;

S¹、S²和D中的苯乙烯类单体单元可以相同或不同；The styrenic monomer units in S ¹ , S ² and D may be the same or different;

其中热塑性弹性体中苯乙烯类单体为所述氢化苯乙烯类-丁二烯类嵌段共聚物重量的50-80重量％。Wherein the styrenic monomer in the thermoplastic elastomer is from 50 to 80% by weight based on the weight of the hydrogenated styrene-butadiene block copolymer.

2)8-45％的单分散无规聚苯乙烯；2) 8-45% monodisperse atactic polystyrene;

本发明的氢化苯乙烯类热塑性弹性体的一个重要特征在于具有高苯乙烯含量。发明人发现，当本发明的热塑性弹性体，尤其是其中的组分(1)嵌段共聚物中苯乙烯类单体的含量高，由此使得热塑性弹性体中苯乙烯的含量高达50-80％时，该嵌段共聚物组分(1)仍表现出典型热塑性弹性体的性质。更出人意料的是，将这样的嵌段共聚物组分(1)与单分散聚苯乙烯通过本发明的方式(非简单物理混合)结合在一起时，可以获得具有亚光和雾面的表面效果的热塑性弹性体，其特别适用于制造优异雾面效果的薄膜、线材和片材等产品。 An important feature of the hydrogenated styrenic thermoplastic elastomer of the present invention is that it has a high styrene content. The inventors have found that when the thermoplastic elastomer of the present invention, especially the component (1) block copolymer therein, has a high content of styrene monomer, thereby making the content of styrene in the thermoplastic elastomer as high as 50-80 At the time of %, the block copolymer component (1) still exhibits the properties of a typical thermoplastic elastomer. More surprisingly, when such a block copolymer component (1) is combined with monodisperse polystyrene by the means of the present invention (non-simple physical mixing), a surface effect having matt and matte surface can be obtained. A thermoplastic elastomer that is particularly suitable for use in the manufacture of films, wires and sheets that have excellent matte finish.

以下将对各组分进行详细描述。Each component will be described in detail below.

组分(1)：氢化苯乙烯-共轭二烯类嵌段共聚物Component (1): hydrogenated styrene-conjugated diene block copolymer

本发明的组分(1)氢化苯乙烯-共轭二烯类嵌段共聚物具有如下结构式：The component (1) hydrogenated styrene-conjugated diene block copolymer of the present invention has the following structural formula:

S¹ _p-D-S² _q  (I)S ¹ _p -DS ² _q (I)

其中：among them:

S¹和S²独立地为苯乙烯类单体聚合嵌段，S¹和S²重量分别占所述嵌段共聚物总重量的8.0-20.0％；S ¹ and S ^{2 are} independently a styrene monomer polymer block, and the weights of S ¹ and S ² are respectively 8.0 to 20.0% by weight of the total weight of the block copolymer;

D为苯乙烯类单体与氢化共轭二烯类单体的共聚嵌段；D is a copolymer block of a styrene monomer and a hydrogenated conjugated diene monomer;

p和q各自独立地为0或1，但不能同时为0；p and q are each independently 0 or 1, but not simultaneously 0;

S¹、S²和D中的苯乙烯类单体单元可以相同或不同。The styrenic monomer units in S ¹ , S ² and D may be the same or different.

在本发明的上述嵌段共聚物热塑性弹性体中，分子结构两端的S¹或S²为普通的聚苯乙烯类嵌段，优选由活性聚合形成，更优选由活性阴离子聚合形成。In the above block copolymer thermoplastic elastomer of the present invention, S ¹ or S ² at both ends of the molecular structure is an ordinary polystyrene block, preferably formed by living polymerization, more preferably by living anionic polymerization.

根据一些优选的实施方案，组分(1)所述苯乙烯类单体单元在嵌段共聚物中的重量百分含量为50-80％，优选60-75％。一般情况下，苯乙烯类单体单元的含量越高，分子链的刚性越高，在含量高于40％的情况下，通常不能够获得理想的弹性体特征。然而本发明通过对嵌段共聚物进行分子结构上的设计，获得了具有高含量的聚苯乙烯类结构单元的热塑性弹性体，其在高达80％的苯乙烯单体单元含量下，仍能够获得热塑性弹性体的性质。According to some preferred embodiments, the styrenic monomer units of component (1) are present in the block copolymer in an amount of from 50 to 80% by weight, preferably from 60 to 75% by weight. In general, the higher the content of the styrene monomer unit, the higher the rigidity of the molecular chain, and in the case where the content is higher than 40%, the desired elastomer characteristics are generally not obtained. However, the present invention obtains a thermoplastic elastomer having a high content of polystyrene structural units by molecularly designing the block copolymer, which is still obtainable at a styrene monomer unit content of up to 80%. The nature of thermoplastic elastomers.

根据一些优选的实施方案，共聚嵌段D如下式所示：According to some preferred embodiments, the copolymer block D is represented by the formula:

-(A_x-B_y)_n-  (II)-(A _x -B _y ) _n - (II)

其中：among them:

A_x为苯乙烯类单体聚合微嵌段，A _x is a styrene monomer polymerization micro block,

B_y为共轭二烯类单体聚合后再经氢化的氢化微嵌段，B _y is a hydrogenated microblock which is polymerized and then hydrogenated by a conjugated diene monomer.

x为1-100，优选1-90，更优选1-70，最优选1-30， x is 1-100, preferably 1-90, more preferably 1-70, most preferably 1-30,

y为1-170，优选1-150，更优选1-90，最优选1-35，y is 1-170, preferably 1-150, more preferably 1-90, most preferably 1-35,

n为30-1100，优选300-1100，更优选650-1100，最优选900-1100，并且n个(A_x-B_y)中每个的共轭二烯烃与苯乙烯类单体的种类和比例可以彼此相同或不同，每个的x可以彼此相同或不同，每个的y可以彼此相同或不同。n is 30-1100, preferably 300-1100, more preferably 650-1100, most preferably 900-1100, and the type of conjugated diene and styrene monomer of each of n (A _x -B _y ) The ratios may be the same or different from each other, and each of x may be the same or different from each other, and each of y may be the same or different from each other.

根据一些优选的实施方案，组分(1)中所述聚合嵌段S¹和S²分别在嵌段共聚物中的重量百分含量为8.0-20.0％，优选8.0-18.0％，更优选8.0-15.0％，最优选10.0-14.0％。当聚合嵌段S¹和S²的重量百分含量低于8.0％时，嵌段共聚物的拉伸强度和定伸模量将显著下降，而S¹和S²的重量百分含量高于20.0％时，嵌段共聚物的硬度会显著升高，弹性明显消失。只有在8.0-20.0％时，嵌段共聚物方能具有较佳的综合性能而满足应用需求。According to some preferred embodiments, the weight percentage of the polymeric blocks S ¹ and S ² in component (1) in the block copolymer is from 8.0 to 20.0%, preferably from 8.0 to 18.0%, more preferably 8.0. -15.0%, most preferably 10.0-14.0%. When the weight percentage of the polymer blocks S ¹ and S ² is less than 8.0%, the tensile strength and the modulus of elongation of the block copolymer will be significantly lowered, and the weight percentages of S ¹ and S ² are higher than At 20.0%, the hardness of the block copolymer increased significantly and the elasticity disappeared remarkably. Only at 8.0-20.0%, the block copolymer can have better overall performance to meet the application needs.

根据一些优选的实施方案，组分(1)的嵌段共聚物的数均分子量为20000-800000g/mol，优选40000-600000g/mol，更优选50000-400000g/mol，最优选100000-300000g/mol。分子量分布指数为1.01-1.5，更优选1.01-1.3，最优选1.01-1.25。According to some preferred embodiments, the block copolymer of component (1) has a number average molecular weight of from 20,000 to 800,000 g/mol, preferably from 40,000 to 600,000 g/mol, more preferably from 50,000 to 400,000 g/mol, most preferably from 100,000 to 300,000 g/mol. . The molecular weight distribution index is from 1.01 to 1.5, more preferably from 1.01 to 1.3, most preferably from 1.01 to 1.25.

可用于本发明中的苯乙烯类单体可以选自苯乙烯、α-甲基苯乙烯、α-乙基苯乙烯和取代的α-烷基苯乙烯(例如对甲基-α-甲基苯乙烯)、对甲基苯乙烯、乙烯基甲苯、乙烯萘和对叔丁基苯乙烯，或它们的混合物。这些之中，苯乙烯、α-甲基苯乙烯或其组合物是最优选的。本文使用的共轭二烯可以是丁二烯，例如1，3-丁二烯，或取代丁二烯，例如异戊二烯、戊间二烯、2，3-二甲基-1，3-丁二烯和1-苯基-1，3-丁二烯，或它们的混合物。这些之中，1，3-丁二烯和异戊二烯，或其组合是最优选的。The styrenic monomer usable in the present invention may be selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, and substituted α-alkylstyrene (for example, p-methyl-α-methylbenzene). Ethylene), p-methylstyrene, vinyl toluene, vinylnaphthalene and p-tert-butylstyrene, or mixtures thereof. Among these, styrene, α-methylstyrene or a combination thereof is most preferred. The conjugated diene used herein may be butadiene such as 1,3-butadiene or substituted butadiene such as isoprene, piperylene, 2,3-dimethyl-1,3 Butadiene and 1-phenyl-1,3-butadiene, or mixtures thereof. Among these, 1,3-butadiene and isoprene, or a combination thereof are most preferred.

本发明的嵌段共聚物热塑性弹性体中，氢化共轭二烯烃嵌段(B_y)的氢化度可以为80-99.99％，优选88-99.0％。氢化度过低会明显降低聚合物的热稳定性，而对其后期应用的热加工成型带来负面影响，氢化度过高会显著提高聚合物合成过程中的氢化反应时间，增加生产成本，降低生产效率。In the block copolymer thermoplastic elastomer of the present invention, the degree of hydrogenation of the hydrogenated conjugated diene block (B _y ) may be from 80 to 99.99%, preferably from 88 to 99.0%. If the degree of hydrogenation is too low, the thermal stability of the polymer will be significantly reduced, which will have a negative impact on the hot working of the later application. The high degree of hydrogenation will significantly increase the hydrogenation reaction time in the polymer synthesis process, increase the production cost and reduce the production cost. Productivity.

根据一些优选的实施方案，组分(1)为线型分子结构，结构式为 S¹-(A_x-B_y)_n-S²，其中S¹、S²、A、B、x、y和n如前所定义。According to some preferred embodiments, component (1) is a linear molecular structure having the formula S ¹ -(A _x -B _y ) _n -S ² , wherein S ¹ , S ² , A, B, x, y and n as defined before.

根据一些优选的实施方案，本发明的组分(1)嵌段共聚物为星型分子结构，结构式为[S¹-(A_x-B_y)_n-S²]_m-R或[S¹-(A_x-B_y)_n]_m-R，其中S¹、S²、A、B、x、y和n如前所定义，R为偶联剂残基，m为星形分子的臂数，为选自3-55的整数，优选为选自3-40的整数，更优选为选自3-15的整数。According to some preferred embodiments, the component (1) block copolymer of the present invention is a star molecular structure having the formula [S ¹ -(A _x -B _y ) _n -S ² ] _m -R or [S ¹ -(A _x -B _y ) _n ] _m -R, wherein S ¹ , S ² , A, B, x, y and n are as defined above, R is a coupling agent residue, and m is an arm of a star molecule The number is an integer selected from 3 to 5, preferably an integer selected from 3 to 40, and more preferably an integer selected from 3 to 15.

根据一些优选的实施方案，偶联剂选自二乙烯基苯、SiCl₄或SnCl₄。According to certain preferred embodiments, the coupling agent is selected from divinylbenzene, SiCl ₄ or SnCl _4.

组分(2)：阴离子聚合的单分散无规聚苯乙烯Component (2): anionically polymerized monodisperse atactic polystyrene

在本发明的一个方案中，阴离子聚合单分散无规聚苯乙烯的数均分子量为20000-50000g/mol，分子量分布指数为1.01-1.20。聚合在使用常规的阴离子方法在溶剂、活化剂及催化剂中进行。In one embodiment of the present invention, the anionically polymerized monodisperse atactic polystyrene has a number average molecular weight of from 20,000 to 50,000 g/mol and a molecular weight distribution index of from 1.01 to 1.20. The polymerization is carried out in a solvent, an activator and a catalyst using a conventional anionic method.

氢化苯乙烯类热塑性弹性体Hydrogenated styrene thermoplastic elastomer

本发明的具有特殊微相结构的氢化苯乙烯类热塑性弹性体在低于60℃具有两个玻璃化转变温度。更具体地，使用差示扫描量热法(DSC)以10K/min升温速度下测定其热转变，在-35℃至-10℃出现一个明显的玻璃化转变，在10℃至30℃出现另一个玻璃化转变。不囿于任何理论，申请人认为-35℃至-10℃的Tg值代表嵌段共聚物S¹ _p-D-S² _q中苯乙烯类单体与氢化共轭二烯类单体的共聚嵌段D内苯乙烯类单体聚合微嵌段和氢化共轭二烯类单体微嵌段均匀交替分布，其与本发明氢化苯乙烯-共轭二烯类嵌段共聚物中第二段聚合分批加入单体混合物进行聚合的方式有关；而10℃至30℃的Tg值代表嵌段共聚物S¹ _p-D-S² _q与灭活所制备的单分散聚苯乙烯通过非简单物理混合的方式结合在一起时，其部分共聚嵌段D与单分散聚苯乙烯在相界面上互相作用后由于共聚嵌段D分子活动性降低而表现出来的玻璃化转变。The hydrogenated styrene-based thermoplastic elastomer having a specific microphase structure of the present invention has two glass transition temperatures at less than 60 °C. More specifically, the thermal transition was measured using differential scanning calorimetry (DSC) at a heating rate of 10 K/min, and a significant glass transition occurred at -35 ° C to -10 ° C, and another occurred at 10 ° C to 30 ° C. A glass transition. Without wishing to be bound by any theory, Applicants believe that the Tg value of -35 ° C to -10 ° C represents the copolymerization block of the styrene monomer and the hydrogenated conjugated diene monomer in the block copolymer S ¹ _p -DS ² _q The D-styrene monomer-polymerized micro-block and the hydrogenated conjugated diene-based monomer micro-block are uniformly and alternately distributed, and the second-stage polymerization group in the hydrogenated styrene-conjugated diene-based block copolymer of the present invention The manner in which the monomer mixture is added in batches for polymerization is related; and the Tg value at 10 ° C to 30 ° C represents the manner in which the block copolymer S ¹ _p -DS ² _{q is} mixed with the inactivated monodisperse polystyrene by non-simple physical mixing. When combined, the partial copolymerization block D and the monodisperse polystyrene interact at the phase interface to exhibit a glass transition due to a decrease in the activity of the copolymer block D molecule.

利用动态力学热分析(DMTA)测定本发明的氢化苯乙烯类热塑性 弹性体的动态机械性能可知，在频率固定为1Hz，升温速率3K/min时，本发明的氢化苯乙烯类热塑性弹性体在-30℃至35℃出现一个明显的内耗峰(tanδ)，内耗峰的峰值在-5℃至10℃，且峰值tanδ≥0.3。Determination of hydrogenated styrenic thermoplastics of the invention by dynamic mechanical thermal analysis (DMTA) The dynamic mechanical properties of the elastomer show that the hydrogenated styrene-based thermoplastic elastomer of the present invention exhibits a significant internal friction peak (tan δ) at -30 ° C to 35 ° C when the frequency is fixed at 1 Hz and the heating rate is 3 K/min. The peak value is between -5 ° C and 10 ° C, and the peak tan δ ≥ 0.3.

本发明的热塑性弹性体的微相分离结构十分特殊，聚苯乙烯在聚合物基体中以分散相形式存在，既存在平均粒径为400-900nm大的聚苯乙烯分散相，又存在平均粒径为10-95nm小的聚苯乙烯分散相。不囿于任何理论，正是由于大的聚苯乙烯分散相使得可见光照射时严重散射，从而在反射光抵消或补偿后显示出亚光或磨砂的效果。The microphase separation structure of the thermoplastic elastomer of the present invention is very special, and polystyrene exists in the form of a dispersed phase in the polymer matrix, and there are both a polystyrene dispersed phase having an average particle diameter of 400-900 nm and an average particle diameter. It is a polystyrene dispersed phase of 10-95 nm. Not to be in any theory, it is precisely because of the large polystyrene dispersed phase that the visible light is heavily scattered, so that after the reflected light is cancelled or compensated, the effect of matt or matte is exhibited.

本发明的另一方面涉及上述氢化苯乙烯类热塑性弹性体的制备方法。该方法包括以下步骤：Another aspect of the invention relates to a process for the preparation of the above hydrogenated styrene-based thermoplastic elastomer. The method includes the following steps:

(i)第一段聚合：使苯乙烯类单体在聚合釜中进行阴离子活性聚合，待单体转化率至少达到95％时，苯乙烯类单体活性种重量含量的30-65％被部分灭活得到单分散的无规聚苯乙烯，在聚合釜中继续加入苯乙烯类单体使未灭活的单体继续聚合或直接进行第二段聚合；(i) First-stage polymerization: anionic living polymerization is carried out in a polymerization vessel in a styrene monomer, and when the monomer conversion rate is at least 95%, 30-65% by weight of the styrene monomer active species is partially Inactivation to obtain monodisperse atactic polystyrene, continue to add styrene monomer in the polymerization vessel to continue the polymerization of the non-inactivated monomer or directly carry out the second stage polymerization;

(ii)第二段聚合：待所述继续加入的苯乙烯类单体的转化率至少达到95％时，向聚合釜中至少分3批加入共轭二烯烃与苯乙烯类单体的混合物进行所述第二段聚合，其中后一批次在前一批次的转化率至少达到95％时加入，每一批次的共轭二烯烃与苯乙烯类单体可以彼此相同或不同；(ii) second stage polymerization: when the conversion rate of the styrene monomer to be continuously added is at least 95%, a mixture of a conjugated diene and a styrene monomer is added to the polymerization tank in at least three portions. The second stage polymerization, wherein the latter batch is added when the conversion rate of the previous batch reaches at least 95%, and each batch of the conjugated diene and the styrene monomer may be the same or different from each other;

(iii)任选的第三段聚合：向聚合釜中加入苯乙烯类单体进行第三段聚合；(iii) optional third stage polymerization: adding a styrenic monomer to the polymerization vessel for the third stage polymerization;

(iv)熟化：待第二段聚合或者在存在第三段聚合时待第三段聚合中单体转化率至少达到95％后，继续在反应釜内熟化，得到线型聚合物；(iv) aging: after the second stage polymerization or in the presence of the third stage polymerization, after the monomer conversion rate in the third stage polymerization reaches at least 95%, the aging is continued in the reactor to obtain a linear polymer;

(v)任选的偶联：向聚合釜中加入偶联剂使反应产物偶联，获得星型聚合物；(v) optional coupling: a coupling agent is added to the polymerization vessel to couple the reaction product to obtain a star polymer;

(vi)将步骤(iv)或(v)中得到的聚苯乙烯胶液转入氢化釜、灭活，并在加氢催化剂存在下对混合物进行氢化。 (vi) The polystyrene gum obtained in the step (iv) or (v) is transferred to a hydrogenation vessel, inactivated, and the mixture is hydrogenated in the presence of a hydrogenation catalyst.

根据一些优选的实施方案，本发明的嵌段共聚物的制备方法中，所述偶联剂选自二乙烯基苯、SiCl₄或SnCl₄。According to some preferred embodiments, in the method of producing a block copolymer of the present invention, the coupling agent is selected from the group consisting of divinylbenzene, SiCl ₄ or SnCl ₄ .

在第一段聚合中通过部分灭活而得到单分散聚苯乙烯使得整个聚合过程耗时短，无需在后期再进行单分散聚苯乙烯胶液的混合、氢化等操作流程。The monodisperse polystyrene obtained by partial inactivation in the first stage polymerization makes the entire polymerization process time-consuming, and it is not necessary to carry out the mixing and hydrogenation operations of the monodisperse polystyrene glue in the later stage.

在第二段聚合中，待第一段聚合转化率至少达到95％时，加入共轭二烯烃/苯乙烯类单体的混合物进行第二段聚合，其中所述单体的混合物分3-60批、优选5-55批、更优选8-40批加入聚合釜中，后一批次在前一批次的转化率至少达到95％时加入。分批加入苯乙烯类单体和共轭二烯类单体的混合物可以使得聚合物链中产生苯乙烯类单体和共轭二烯类单体的微嵌段。优选地，分批加入的所述单体的混合物每一批的重量相等。优选地，分批加入的所述单体的混合物每一批的单体比例也相同。在每一批次中，混合单体中苯乙烯类单体重量百分含量可以为20.0-70.0％，优选30.0-60.0％。在第二段聚合中，所述混合单体中，苯乙烯类单体重量百分含量可以为20.0-64.0％，优选30.0-60.0％，更优选40.0-60.0％。In the second stage polymerization, when the first stage polymerization conversion rate is at least 95%, a mixture of conjugated diene/styrene monomers is added for the second stage polymerization, wherein the mixture of the monomers is divided into 3-60. Batches, preferably 5-55 batches, more preferably 8-40 batches, are added to the polymerization vessel, and the latter batch is added at a conversion of at least 95% of the previous batch. The addition of a mixture of a styrenic monomer and a conjugated diene monomer in portions allows the production of microblocks of styrenic monomers and conjugated diene monomers in the polymer chain. Preferably, the batch of the monomer mixture added in portions is equal in weight per batch. Preferably, the mixture of monomers fed in batches also has the same monomer ratio per batch. In each batch, the weight percentage of styrenic monomer in the mixed monomer may range from 20.0 to 70.0%, preferably from 30.0 to 60.0%. In the second stage polymerization, the styrene monomer may have a weight percentage of the styrene monomer of from 20.0 to 64.0%, preferably from 30.0 to 60.0%, more preferably from 40.0 to 60.0%.

用作聚合载体的溶剂可以是不与形成的聚合物的活性阴离子链端反应、容易在商业聚合设备中处理并且为产物聚合物提供合适的溶解度特性的任何烃。例如，通常缺乏可电离的氢的非极性脂族烃构成特别合适的溶剂。通常使用的是环状烷烃，例如环戊烷、环己烷、环庚烷和环辛烷，所有这些是相对非极性的。其他合适的溶剂将是本领域技术人员已知的并且可被选择以在给定的工艺条件设置下有效地发挥作用，其中温度和含水量是被考虑的最主要的因素。根据一些优选的实施方案，本发明的嵌段共聚物的制备方法中，其中所述第一段聚合在选自环己烷、正己烷、苯、甲苯、二甲苯庚烷，或其混合物的溶剂中进行。优选地，所述溶剂的总水含量低于30ppm。The solvent used as the polymeric carrier can be any hydrocarbon that does not react with the living anionic chain ends of the formed polymer, is readily handled in commercial polymerization equipment, and provides suitable solubility characteristics to the product polymer. For example, non-polar aliphatic hydrocarbons which generally lack ionizable hydrogen constitute a particularly suitable solvent. Commonly used are cyclic alkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, all of which are relatively non-polar. Other suitable solvents will be known to those skilled in the art and can be selected to function effectively under the given set of process conditions, with temperature and water content being the most important factors to be considered. According to some preferred embodiments, in the method for producing a block copolymer of the present invention, wherein the first stage is polymerized in a solvent selected from the group consisting of cyclohexane, n-hexane, benzene, toluene, xylene heptane, or a mixture thereof In progress. Preferably, the solvent has a total water content of less than 30 ppm.

本发明中的阴离子聚合引发剂包括例如烷基锂化合物和其它有机锂化合物，例如仲丁基锂、正丁基锂、叔丁基锂、戊基锂等，包括二引 发剂如间二异丙烯基苯的二仲丁基锂加合物。美国专利6492469中公开了其它此类二引发剂。在各种聚合引发剂中，正丁基锂或仲丁基锂是优选的。所述引发剂可以以基于每个希望的聚合物链一个引发剂分子计算的量用于聚合混合物(包括单体和溶剂)中。所述锂引发剂方法是公知的，并且被公开在例如美国专利4039593中，这些描述通过引用结合在本文中。The anionic polymerization initiator in the present invention includes, for example, an alkyllithium compound and other organolithium compounds such as sec-butyllithium, n-butyllithium, t-butyllithium, pentyllithium, etc., including A hair agent such as di-sec-butyl lithium adduct of m-isopropenylbenzene. Other such diinitiators are disclosed in U.S. Patent 6,492,469. Among various polymerization initiators, n-butyllithium or sec-butyllithium is preferred. The initiator can be used in the polymerization mixture (including monomers and solvents) in an amount calculated based on one initiator molecule per desired polymer chain. The lithium initiator process is well known and is disclosed, for example, in U.S. Patent 4,039,593, the disclosure of which is incorporated herein by reference.

单体转化率通过对聚合反应过程中的提取物利用气相色谱法进行测定，本发明人发现，在单体转化率为95％以上时，本发明聚合物的分子结构方能满足发明所描述的设计要求。The monomer conversion rate is determined by gas chromatography for the extract during the polymerization reaction, and the inventors have found that the molecular structure of the polymer of the present invention can satisfy the description of the invention when the monomer conversion rate is 95% or more. Design requirements.

可用于本发明中的多种偶联剂是本领域中已知的，并且包括例如二卤代烷烃，卤化硅，硅氧烷，多官能的环氧化物，包括间-二乙烯基苯等在内的多链烯基化合物，包括烷氧基硅烷、烷基硅烷、烷基-烷氧基硅烷等在内的二氧化硅化合物，包括己二酸二甲酯等在内的一元醇与羧酸的酯，和环氧化的油。优选的是四烷氧基硅烷，例如四乙氧基硅烷(TEOS)和四甲氧基硅烷；烷基三烷氧基硅烷，例如甲基三甲氧基硅烷(MTMQ；脂肪族二酯，例如己二酸二甲酯和己二酸二乙酯；和二缩水甘油基芳族环氧化合物，例如得自双酚A与环氧氯丙烷的反应的二缩水甘油基醚。当希望随后进行加氢或选择性加氢时，偶联剂的选择应使得任何残留的未反应的偶联剂、结合到聚合物链中的偶联剂残基或偶联反应的副产物不影响所述加氢反应。在本发明的方法中，偶联剂优选地选自二乙烯基苯、SiCl₄或SnCl₄。A wide variety of coupling agents useful in the present invention are known in the art and include, for example, dihaloalkanes, silicon halides, siloxanes, polyfunctional epoxides, including m-divinylbenzene, and the like. a polyalkenyl compound, a silica compound including an alkoxysilane, an alkylsilane, an alkyl-alkoxysilane, or the like, a monohydric alcohol and a carboxylic acid including dimethyl adipate and the like. Ester, and epoxidized oil. Preferred are tetraalkoxysilanes such as tetraethoxysilane (TEOS) and tetramethoxysilane; alkyltrialkoxysilanes such as methyltrimethoxysilane (MTMQ; aliphatic diesters such as Dimethyl dicarboxylate and diethyl adipate; and diglycidyl aromatic epoxy compounds, such as diglycidyl ethers derived from the reaction of bisphenol A with epichlorohydrin. When it is desired to subsequently hydrogenate or In the selective hydrogenation, the coupling agent is selected such that any residual unreacted coupling agent, coupling agent residues incorporated into the polymer chain or by-products of the coupling reaction do not affect the hydrogenation reaction. in the method of the present invention, the coupling agent is preferably selected from divinylbenzene, SiCl ₄ or SnCl _4.

在制备偶联的嵌段共聚物的本发明实施方案中，将偶联剂以产生具有希望的臂数分布的偶联聚合物的摩尔比加入到活性聚合物中。所述偶联剂可以以纯化合物的形式添加，或者为了便于计量，可以被稀释在惰性溶剂中。添加方式可能对臂数分布有影响。偶联之后，通常不需要终止反应。根据一些优选的实施方案，本发明的嵌段共聚物的制备方法得到的星型聚合物具有3-55个臂，优选3-40个臂，更优选8-35个臂。In an embodiment of the invention for preparing a coupled block copolymer, the coupling agent is added to the living polymer in a molar ratio to produce a coupled polymer having a desired arm number distribution. The coupling agent may be added in the form of a pure compound or may be diluted in an inert solvent for ease of metering. The way of adding may have an effect on the number of arms. After coupling, it is usually not necessary to terminate the reaction. According to some preferred embodiments, the star polymer obtained by the process for producing the block copolymer of the present invention has from 3 to 5 arms, preferably from 3 to 40 arms, more preferably from 8 to 35 arms.

在其中生产非偶联嵌段共聚物的本发明实施方案中，通过添加终止剂来停止聚合。阴离子聚合经常通过加入水以便以氢氧化锂(LiOH)的 形式从聚合物链末端移除锂或者通过加入醇(ROH)以便以醇锂(LiOR)的形式移除锂来终止。以相对于活性链末端摩尔过量的量添加终止剂。当希望随后进行加氢或选择性加氢时，应该选择终止剂的类型和/或量，以使得残留的终止剂或终止反应副产物不影响加氢。In an embodiment of the invention in which a non-coupled block copolymer is produced, the polymerization is stopped by the addition of a terminator. Anionic polymerization is often carried out by adding water to lithium hydroxide (LiOH) The form is terminated by removing lithium from the end of the polymer chain or by adding alcohol (ROH) to remove lithium in the form of lithium alkoxide (LiOR). The terminator is added in an amount relative to the molar excess of the end of the living chain. When it is desired to carry out subsequent hydrogenation or selective hydrogenation, the type and/or amount of terminator should be chosen such that residual terminator or termination reaction by-product does not affect hydrogenation.

第一段聚合中，对活性种部分灭活时采用的灭活剂为2，6-二叔丁基-4-甲基苯酚；在锂系阴离子聚合中，一般采用强质子给予体作为灭活剂，如水、醇等。然而若采用这些传统灭活剂进行部分灭活会对未灭活部分的链增长带来明显的不可控性，甚至完全降低活性种的反应活性。发明人发现采用2，6-二叔丁基-4-甲基苯酚不会对未灭活活性种的继续链增长带来负面影响。采用2，6-二叔丁基-4-甲基苯酚时，先将其与不含水的惰性聚合溶剂进行混合，然后在第一段聚合终点直接注入聚合釜中即可。In the first stage of polymerization, the inactivating agent used in the partial inactivation of the active species is 2,6-di-tert-butyl-4-methylphenol; in the lithium-based anionic polymerization, a strong proton donor is generally used as the inactivation. Agents such as water, alcohol, and the like. However, partial inactivation with these traditional inactivating agents can cause significant uncontrollable chain growth in the inactivated portion, and even completely reduce the reactivity of the active species. The inventors have found that the use of 2,6-di-tert-butyl-4-methylphenol does not adversely affect the continued chain growth of the non-inactivated active species. When 2,6-di-tert-butyl-4-methylphenol is used, it is first mixed with an inert polymerization solvent containing no water, and then directly injected into the polymerization vessel at the end point of the first stage polymerization.

可以通过现有技术中已知的若干加氢或选择性加氢方法中的任何一种来进行加氢。例如，使用诸如在例如US专利No.3595942、3634549、3670054、3700633等中教导的方法已经完成了这样的加氢，所述专利公开的内容通过引用结合在本文中。优选地，本发明中使用的催化剂包括钛基催化剂体系，优选为茂钛化合物。根据一些优选的实施方案，其中所述氢化步骤的氢化反应温度为60-140℃，压力为0.8-2.2MPa，时间为60-200min。Hydrogenation can be carried out by any of several hydrogenation or selective hydrogenation processes known in the art. Such hydrogenation has been accomplished, for example, using methods such as those taught in, for example, U.S. Patent Nos. 3,359,942, 3,634,549, 3,760, 054, 3,700, 633, the disclosure of which is incorporated herein by reference. Preferably, the catalyst used in the present invention comprises a titanium-based catalyst system, preferably a titanocene compound. According to some preferred embodiments, wherein the hydrogenation step has a hydrogenation reaction temperature of from 60 to 140 ° C, a pressure of from 0.8 to 2.2 MPa, and a time of from 60 to 200 minutes.

优选地，加氢操作的进行应使得本发明的嵌段共聚物热塑性弹性体中，氢化共轭二烯烃嵌段的氢化度为80-99.99％，优选88-99.0％。氢化度过低会明显降低聚合物的热稳定性，而对其后期应用的热加工成型带来负面影响，氢化度过高会显著提高聚合物合成过程中的氢化反应时间，增加生产成本，降低生产效率。Preferably, the hydrogenation operation is carried out such that the hydrogenated degree of the hydrogenated conjugated diene block in the block copolymer thermoplastic elastomer of the present invention is from 80 to 99.99%, preferably from 88 to 99.0%. If the degree of hydrogenation is too low, the thermal stability of the polymer will be significantly reduced, which will have a negative impact on the hot working of the later application. The high degree of hydrogenation will significantly increase the hydrogenation reaction time in the polymer synthesis process, increase the production cost and reduce the production cost. Productivity.

示例性的制备本发明的氢化苯乙烯类热塑性弹性体的方案如下：An exemplary scheme for preparing the hydrogenated styrenic thermoplastic elastomer of the present invention is as follows:

a)对于线形分子结构：a) For linear molecular structures:

首先在聚合釜内加入溶剂、活化剂，升温到50-100℃；然后将苯乙烯类单体送入聚合釜内，并将计量好的催化剂加入进行第一段聚合，待单体转化率至少达到95％时，加入灭活剂对苯乙烯类单体活性种重量含 量30-65％的活性种进行灭活，然后继续加入苯乙烯类单体进行聚合；待后加入的苯乙烯类单体的转化率至少达到95％时，加入共轭二烯烃/苯乙烯类单体的混合物进行第二段聚合，在第二段聚合中混合单体分3-40批加入到聚合釜内进行反应，即第二段聚合中又分为3-40批进行聚合反应，反应时每一批的转化率至少达到95％时再加入下一批混合单体进行反应，直到所有批次的混合单体依次反应完全；第二段聚合完成后，将苯乙烯类单体送入聚合釜内进行第三段聚合，待第三段单体转化率至少达到95％后，继续在反应釜内熟化20-120min；随后将胶液泵入氢化釜灭活，在加氢催化剂存在下，利用氢气进行氢化，氢化反应温度为60-140℃，压力为0.8-2.2MPa，时间为60-200min；最后对产物进行凝聚和干燥得到热塑性弹性体成品。First, a solvent and an activator are added to the polymerization vessel, and the temperature is raised to 50-100 ° C; then the styrene monomer is fed into the polymerization vessel, and the metered catalyst is added for the first stage polymerization, and the monomer conversion rate is at least When 95% is reached, the inactivating agent is added to the weight of the active species of the styrene monomer. 30-65% of the active species are inactivated, and then the styrene monomer is continuously added for polymerization; when the conversion of the styrene monomer to be added is at least 95%, the conjugated diene/styrene is added. The monomer mixture is subjected to the second stage polymerization, and in the second stage polymerization, the mixed monomer is added to the polymerization tank in a batch of 3-40 batches for reaction, that is, the second stage polymerization is further divided into 3-40 batches for polymerization reaction. When the conversion rate of each batch reaches at least 95%, the next batch of mixed monomers is added to carry out the reaction until all the mixed monomers are completely reacted; after the second polymerization is completed, the styrene monomer is fed. The third stage polymerization is carried out in the polymerization vessel. After the third stage monomer conversion rate reaches at least 95%, the reactor is further aged in the reactor for 20-120 min; then the glue is pumped into the hydrogenation vessel to be inactivated, in the presence of a hydrogenation catalyst. Hydrogenation is carried out by using hydrogen gas, the hydrogenation reaction temperature is 60-140 ° C, the pressure is 0.8-2.2 MPa, and the time is 60-200 min; finally, the product is coagulated and dried to obtain a thermoplastic elastomer finished product.

b)对于星形分子结构：b) For star molecular structures:

首先在聚合釜内加入溶剂、活化剂，升温到50-100℃；然后将苯乙烯类单体送入聚合釜内，并将计量好的催化剂加入进行第一段聚合，待单体转化率至少达到95％时，加入灭活剂对苯乙烯类单体活性种重量含量30-65％的活性种进行灭活，然后继续加入苯乙烯类单体进行聚合；待后加入的苯乙烯类单体的转化率至少达到95％时，加入共轭二烯烃/苯乙烯类单体的混合物进行第二段聚合，在第二段聚合中混合单体分3-40批加入到聚合釜内进行反应，即第二段聚合中又分为3-40批进行聚合反应，反应时每一批的转化率达到至少95％时再加入下一批混合单体进行反应，直到所有批次的混合单体依次反应完全；第二段区聚合完成后，将苯乙烯类单体送入聚合釜内进行第三段聚合，待第三段单体转化率达到至少95％后，继续在反应釜内熟化20-120min；随后利用二乙烯基苯对聚合物活性分子链进行偶联，得到臂数为3-55的等臂长星形分子；若为了得到臂数为3-4的星形分子，也可以利用SiCl₄和SnCl₄对聚合物活性分子链进行偶联；得到分子结构为[S-(A_x-B_y)_n-S]_m-R的星形嵌段共聚物；若在第二段聚合结束后，直接进行偶联则得到分子结构为[S-(A_x-B_y)_n]_m-R的星形嵌段共聚物；随后将胶液泵入氢化釜灭活，在加氢催化剂存在下，利用氢气进行氢化，氢化反应温度为60-140℃，压力为0.8-2.2MPa，时 间为60-200min；最后对产物进行凝聚和干燥得到热塑性弹性体成品。First, a solvent and an activator are added to the polymerization vessel, and the temperature is raised to 50-100 ° C; then the styrene monomer is fed into the polymerization vessel, and the metered catalyst is added for the first stage polymerization, and the monomer conversion rate is at least When 95% is reached, the inactivater is added to inactivate the active species of 30-65% by weight of the styrene monomer active species, and then the styrene monomer is continuously added for polymerization; the styrene monomer to be added later is added. When the conversion rate is at least 95%, a mixture of conjugated diene/styrene monomer is added for the second stage polymerization, and in the second stage polymerization, the mixed monomer is added to the polymerization tank for 3-40 batches to carry out the reaction. That is, in the second stage polymerization, the polymerization is further divided into 3-40 batches, and when the conversion rate of each batch reaches at least 95%, the next batch of mixed monomers is added to carry out the reaction until all the mixed monomers are sequentially The reaction is complete; after the second stage polymerization is completed, the styrene monomer is sent to the polymerization vessel for the third stage polymerization, and after the third stage monomer conversion rate reaches at least 95%, the aging is continued in the reactor. 120 min; subsequent use of divinylbenzene The polymer active molecular chain is coupled to obtain an equipotentially long star molecule with a number of arms of 3-55; if a star molecule with a number of arms of 3-4 is obtained, the activity of the polymer can also be utilized by SiCl ₄ and SnCl _{4 .} The molecular chain is coupled; a star block copolymer having a molecular structure of [S-(A _x -B _y ) _n -S] _m -R is obtained; if the second stage polymerization is completed, the coupling is directly performed. a star block copolymer having a molecular structure of [S-(A _x -B _y ) _n ] _m -R; the gum is then pumped into a hydrogenation vessel to be inactivated, hydrogenated by hydrogenation in the presence of a hydrogenation catalyst, hydrogenation The reaction temperature is 60-140 ° C, the pressure is 0.8-2.2 MPa, and the time is 60-200 min; finally, the product is coagulated and dried to obtain a finished thermoplastic elastomer.

发明人意外地发现了一类新型氢化苯乙烯-共轭二烯类嵌段共聚物(组分(1))，它是一种苯乙烯-氢化共轭二烯嵌段共聚物，该聚合物为一类特殊结构的嵌段SEB。令人惊讶的是当该类嵌段SEB中苯乙烯类单体的总质量含量达到50-80％时，该聚合物仍表现出典型热塑性弹性体的性质，这完全与传统常识相悖。另一方面，由于苯乙烯单体的成本明显低于丁二烯，该新型氢化苯乙烯-共轭二烯类嵌段共聚物相比传统SEBS有明显的成本优势。虽然新型氢化苯乙烯-共轭二烯类嵌段共聚物(组分1)中苯乙烯单体的含量很高(＞50％)，但原子力显微镜的研究发现聚苯乙烯相(PS)仍以颗粒的形式作为分散微相存在，平均粒径为12-90nm。The inventors have unexpectedly discovered a novel class of hydrogenated styrene-conjugated diene block copolymers (component (1)) which is a styrene-hydrogenated conjugated diene block copolymer, the polymer It is a special type of block SEB. Surprisingly, when the total mass content of the styrenic monomer in the block SEB reaches 50-80%, the polymer still exhibits the properties of a typical thermoplastic elastomer, which is completely contrary to conventional wisdom. On the other hand, since the cost of styrene monomer is significantly lower than that of butadiene, the novel hydrogenated styrene-conjugated diene block copolymer has a significant cost advantage over conventional SEBS. Although the content of styrene monomer in the novel hydrogenated styrene-conjugated diene block copolymer (component 1) is very high (>50%), atomic force microscopy studies have found that the polystyrene phase (PS) still The form of the particles exists as a dispersed microphase having an average particle diameter of 12 to 90 nm.

另外，发明人意外地发现若将第一段阴离子聚苯乙烯活性种部分灭 活后继续进行嵌段聚合，得到的产物仍为优良的热塑性弹性体，其各方面性能与氢化苯乙烯-共轭二烯类嵌段共聚物相当。后期结构研究发现该热塑性弹性体中的微相分离结构十分特殊，PS在聚合物基体中以分散相形式存在，但既存在平均粒径为400-900nm大的PS分散相，又存在平均粒径为10-95nm小的PS分散相。Further, the inventors have surprisingly found that the inactivation of the active species if the first segment portion anionic polystyrene block polymerization proceeds, the resulting product is still thermoplastic elastomer excellent in all aspects of its performance and hydrogenated styrene - conjugated The diene block copolymer is equivalent. Later structural studies have found that the microphase separation structure in the thermoplastic elastomer is very special. PS exists in the form of a dispersed phase in the polymer matrix, but there are both PS dispersed phase with average particle diameter of 400-900 nm and average particle size. It is a PS dispersed phase of 10 to 95 nm.

令人惊奇的这种特殊的相结构所带来的有益技术效果是，该热塑性弹性体表面具有极佳的雾面效果，且雾面的效果十分细腻。该产物在生产薄膜、线材和片材等产品时同样具有极佳的雾面效果，达到了一种意想不到的应用效果。不囿于任何理论，我们认为大的PS分散相是该热塑性弹性体中产生细腻雾面效果的直接原因。The surprising technical effect of this particular phase structure is that the surface of the thermoplastic elastomer has an excellent matte finish and the matte finish is very delicate. The product also has an excellent matte effect in the production of films, wires and sheets, and achieves an unexpected application effect. Without being bound by any theory, we believe that a large PS dispersed phase is the direct cause of the fine matte effect in the thermoplastic elastomer.

应用研究发现，利用本发明所公开的新型氢化苯乙烯-共轭二烯类嵌段共聚物(组分1)制备薄膜、线材和片材等产品时，无论与其它一定量任何添加剂(各种无机填料，润滑剂，抗氧剂，增塑剂等)相配合，或与其它一定量共聚物共混，或者动态硫化，薄膜、线材和片材等产品均只能得到高光泽的表面效果。有些情况下，当添加剂的量特别大时(如无机填料SiO2的量达到60-70％)或其它共聚物的量特别大时(如PA、PC的量达到50-60％)、或者深度动态硫化后，也可以得到有限的雾面效果，但此时该新型氢化苯乙烯-共轭二烯类嵌段共聚物已失去了热塑性弹性体 的性质，且其它各种性能，如弹性，流动性，强度等也均有较大的改变。Application studies have found that when using the novel hydrogenated styrene-conjugated diene block copolymer (component 1) disclosed in the present invention to prepare films, wires and sheets, etc., regardless of any other amount of any additives (various Inorganic fillers, lubricants, antioxidants, plasticizers, etc., or blended with other certain amounts of copolymers, or dynamically vulcanized, films, wires and sheets can only achieve high gloss surface effects. In some cases, when the amount of additives is particularly large (such as the amount of inorganic filler SiO2 reaches 60-70%) or the amount of other copolymers is particularly large (such as PA, PC amount of 50-60%), or depth dynamics After vulcanization, a limited matte effect can also be obtained, but at this time the novel hydrogenated styrene-conjugated diene block copolymer has lost the thermoplastic elastomer. The nature, and various other properties, such as elasticity, fluidity, strength, etc. also have a large change.

我们同时考虑将各种分子量的阴离子聚合PS或自由基聚合PS与本发明所公开的新型氢化苯乙烯-共轭二烯类嵌段共聚物(组分1)直接共混，无论它们各自的比例如何改变，采用何种共混方法(双螺杆挤出，密炼和溶液混合后再凝聚干燥等)，均无法得到雾面效果，而且始终表现为高光表面。We also consider directly blending anionically polymerized PS or radically polymerized PS of various molecular weights with the novel hydrogenated styrene-conjugated diene block copolymers (component 1) disclosed herein, regardless of their respective ratios. How to change, what kind of blending method ( twin-screw extrusion, mixing and solution mixing, coagulation and drying, etc.), can not get the matte effect, and always behave as a high-gloss surface.

薄膜、线材和片材等产品在许数应用场合需要雾面的表面效果，给人一种柔和的视觉效果。本发明所公开具有特殊微相结构的氢化苯乙烯类热塑性弹性体本身就具有雾面效果，其效果是与生俱来的，不是由添加剂，与其它共聚物共混，或者动态硫化等方式产生的。Films, wires and sheets require matte surface effects in a number of applications, giving a soft visual effect. The hydrogenated styrene-based thermoplastic elastomer disclosed in the present invention having a special microphase structure has a matte effect by itself, and the effect is inherent, not by additives, blending with other copolymers, or by dynamic vulcanization. of.

进一步的研究发现，该特殊微相结构的氢化苯乙烯类热塑性弹性体具有极佳的皮肤触感。主要表现为皮肤接触时十分干爽，而普通SEBS在皮肤接触时总会给人粘手和油腻感。Further studies have found that the hydrogenated styrenic thermoplastic elastomer of this particular microphase structure has an excellent skin feel. The main manifestation is that the skin is very dry when it comes into contact, and the common SEBS always gives a sticky and greasy feel when it comes into contact with the skin.

实施例Example

以下通过具体实施例和比较例对本发明做进一步的说明，但本发明并不受以下实施例所限。The present invention will be further illustrated by the following specific examples and comparative examples, but the present invention is not limited by the following examples.

一、实施例和对比例中热塑性弹性体的基本物性按以下标准进行测定：1. The basic physical properties of the thermoplastic elastomer in the examples and comparative examples were determined according to the following criteria:

拉伸性能按照ASTM D412进行测试，拉伸速率250mm/min，测试样品为聚合物甲苯溶液涂布薄膜；The tensile properties were tested in accordance with ASTM D412, the tensile rate was 250 mm/min, and the test sample was a polymer toluene solution coated film;

硬度(shore A)按照ASTM 2240进行测试，读数时间为10s，测试样品为聚合物177℃模压成型片材；Hardness (shore A) was tested in accordance with ASTM 2240 with a reading time of 10 s and the test sample was a polymer molded sheet of 177 ° C;

熔融指数按照ASTM D 1238进行测试，条件为230℃，5kg；The melt index is tested in accordance with ASTM D 1238, at 230 ° C, 5 kg;

片材雾面细腻程度测试：测试样品为聚合物177℃模压成型片材，目测；Sheet matte finish test: test sample is polymer 177 ° C molded sheet, visual inspection;

线材雾面细腻程度测试：测试样品为单螺杆挤出机直接从圆口模挤出的圆柱状线材，直径2.5-4mm，目测；Wire matte finish test: The test sample is a cylindrical wire extruded directly from a round die with a single screw extruder, diameter 2.5-4mm, visual inspection;

片材触感测试：人裸手直接接触测试，测试样品为聚合物177℃模 压成型片材。Sheet touch test: direct contact test of human bare hands, test sample is polymer 177 ° C mode Press-formed sheet.

二、实施例和对比例中热塑性弹性体的结构表征按以下方法进行测定：2. Structural Characterization of Thermoplastic Elastomers in the Examples and Comparative Examples were determined as follows:

聚合物分子量和分子量分布利用Waters GPC进行测定，流动相为四氢呋喃；The molecular weight and molecular weight distribution of the polymer were measured by Waters GPC, and the mobile phase was tetrahydrofuran;

聚合物苯乙烯单体和氢化共轭二烯单体相对质量含量、氢化共轭二烯嵌段氢化度利用Brucker 600MHz核磁共振光谱仪进行测定，利用的是氢谱；The relative mass content of the polymer styrene monomer and the hydrogenated conjugated diene monomer and the hydrogenation degree of the hydrogenated conjugated diene block were measured by a Brucker 600 MHz nuclear magnetic resonance spectrometer using a hydrogen spectrum;

聚合物的热转变利用NETZCH DSC 204F3进行测定，速率为10K/min，温度范围为-90-150℃；The thermal transition of the polymer was measured using NETZCH DSC 204F3 at a rate of 10 K/min and a temperature range of -90-150 ° C;

聚合物的动态机械行为利用TA DMTA进行测定，频率固定为1Hz，升温速率3K/min，温度扫描范围-80-200℃；The dynamic mechanical behavior of the polymer was measured by TA DMTA, the frequency was fixed at 1 Hz, the heating rate was 3 K/min, and the temperature scanning range was -80-200 ° C;

聚合物的微观相分离行为利用NanoScope III AFM原子力显微镜进行测定，敲击模式，扫描频率为1Hz，测试样品为聚合物甲苯稀溶液在云母片上铸膜而成。The microscopic phase separation behavior of the polymer was measured by a NanoScope III AFM atomic force microscope. The tapping mode was performed at a frequency of 1 Hz. The test sample was formed by casting a film of a polymer toluene solution on a mica sheet.

实施例1Example 1

首先在聚合釜内加入溶剂环己烷(含水量22ppm)、活化剂，升温到70℃；然后将苯乙烯(占单体总重量的27.6％)送入聚合釜内，并将计量好的催化剂正丁基锂加入进行第一段聚合，待单体转化率至少达到95％时，加入2，6-二叔丁基-4-甲基苯酚对占活性种50％的活性种进行灭活，然后继续加入苯乙烯(占单体总重量的3.4％)进行聚合；待后加入的苯乙烯的转化率至少达到95％时，加入丁二烯烃/苯乙烯的混合物(苯乙烯的相对重量含量为混合物的61.3％)进行第二段聚合，在第二段聚合中混合单体分15批(每批的重量相等)加入到聚合釜内进行反应，反应时每一段的转化率至少达到95％时再加入下一批混合单体进行反应，直到所有批次的混合单体依次反应完全；第二段聚合完成后，将苯乙烯(占单体总重量的17.2％)送入聚合釜内进行第三段聚合，待第三段单体转化率至少达到95％后，继续在反应釜内熟化60min；得到线形分子结构的产 物。随后将混合胶液泵入氢化釜，在加氢催化剂茂钛化合物存在下，利用氢气对混合物进行氢化，氢化反应温度为100℃，压力为2.2MPa，时间为160min；最后对产物进行凝聚和干燥得到热塑性弹性体成品。First, a solvent cyclohexane (water content 22 ppm) and an activator were added to the polymerization vessel, and the temperature was raised to 70 ° C; then styrene (27.6% by weight of the total monomer) was fed into the polymerization vessel, and the catalyst was metered. n-Butyllithium is added for the first stage polymerization. When the monomer conversion rate is at least 95%, 2,6-di-tert-butyl-4-methylphenol is added to inactivate 50% of the active species. Then continue to add styrene (3.4% by weight of the total monomer) for polymerization; when the conversion of styrene to be added is at least 95%, a mixture of butadiene/styrene is added (the relative weight of styrene is 61.3% of the mixture is subjected to the second stage polymerization, and in the second stage polymerization, the mixed monomer is divided into 15 batches (the weight of each batch is equal) and added to the polymerization tank for the reaction, and the conversion rate of each stage at the time of the reaction is at least 95%. The next batch of mixed monomers is added to carry out the reaction until all the mixed monomers in the batch are completely reacted; after the second stage polymerization is completed, styrene (17.2% of the total weight of the monomers) is sent to the polymerization kettle for the first Three-stage polymerization, until the third stage monomer conversion rate is at least After 95%, and aged for 60min in a reactor; linear molecular structure have been produced Things. Subsequently, the mixed glue is pumped into the hydrogenation reactor, and the mixture is hydrogenated by hydrogen in the presence of a hydrogenation catalyst titanocene compound, the hydrogenation reaction temperature is 100 ° C, the pressure is 2.2 MPa, and the time is 160 min; finally, the product is coagulated and dried. A finished thermoplastic elastomer is obtained.

实施例2Example 2

首先在聚合釜内加入溶剂环己烷(含水量10ppm)、活化剂，升温到100℃；然后将苯乙烯(占单体总重量的40％)送入聚合釜内，并将计量好的催化剂仲丁基锂加入进行第一段聚合，待单体转化率至少达到95％时，加入2，6-二叔丁基-4-甲基苯酚对占活性种50％的部分活性种进行灭活，加入丁二烯烃/苯乙烯的混合物(苯乙烯的相对重量含量为混合物的36.4％)进行第二段聚合，在第二段聚合中混合单体分25批(每批的重量相等)加入到聚合釜内进行反应，反应时每一段的转化率至少达到95％时再加入下一批混合单体进行反应，直到所有批次的混合单体依次反应完全；第二段聚合完成后，将苯乙烯(占单体总重量的20％)送入聚合釜内进行第三段聚合，待第三段单体转化率至少达到95％后，继续在反应釜内熟化120min；随后利用SiCl₄对聚合物活性分子链进行偶联，得到臂数为4的等臂长星形分子；最终得到分子结构为[S-(A_x-B_y)_n-S]_m-R的星形嵌段共聚物；随后将混合胶液泵入氢化釜，在加氢催化剂茂钛化合物存在下，利用氢气对混合物进行氢化，氢化反应温度为60℃，压力为1.0MPa，时间为200min；最后对产物进行凝聚和干燥得到热塑性弹性体成品。First, a solvent cyclohexane (water content 10 ppm) and an activator were added to the polymerization vessel, and the temperature was raised to 100 ° C; then styrene (40% by weight of the total monomer) was fed into the polymerization vessel, and the catalyst was metered. Adding sec-butyllithium to the first stage of polymerization, when the monomer conversion rate is at least 95%, adding 2,6-di-tert-butyl-4-methylphenol to inactivate some active species of 50% of the active species Adding a mixture of butadiene/styrene (the relative weight content of styrene is 36.4% of the mixture) for the second stage polymerization, and mixing the monomers in the second stage polymerization into 25 batches (the weight of each batch is equal) is added to The reaction is carried out in the polymerization vessel. When the conversion rate of each stage reaches at least 95%, the next batch of mixed monomers is added to carry out the reaction until all the mixed monomers are completely reacted; after the second stage polymerization is completed, the benzene is completed. Ethylene (20% of the total weight of the monomer) is sent to the polymerization vessel for the third stage polymerization. After the third stage monomer conversion rate reaches at least 95%, the aging is continued for 120 minutes in the reactor; then the polymerization is performed by SiCl ₄ The active molecular chain is coupled to obtain 4 arms Other arm length star molecule; molecular structure finally obtained _{[S- (A x -B y)} n -S] _m -R a radial block copolymer; glue mixture is then pumped into the hydrogenation reactor, the hydrogenation In the presence of the catalyst titanocene compound, the mixture is hydrogenated with hydrogen, the hydrogenation reaction temperature is 60 ° C, the pressure is 1.0 MPa, and the time is 200 min. Finally, the product is coagulated and dried to obtain a finished thermoplastic elastomer.

实施例3Example 3

首先在聚合釜内加入溶剂正己烷(含水量28ppm)、活化剂，升温到50℃；然后将α-甲基苯乙烯(占单体总重量的40％)送入聚合釜内，并将计量好的催化剂正丁基锂加入进行第一段聚合，待单体转化率至少达到95％时，加入2，6-二叔丁基-4-甲基苯酚对占活性种50％的部分活性种进行灭活，加入异戊二烯/苯乙烯的混合物(苯乙烯的相对重量含量为混合物的33.3％)进行第二段聚合，在第二段聚合中混合单体分5批(每批 的重量相等)加入到聚合釜内进行反应，反应时每一段的转化率至少达到95％时再加入下一批混合单体进行反应，直到所有批次的混合单体依次反应完全；第二段聚合完成后，将α-甲基苯乙烯(占单体总重量的20％)送入聚合釜内进行第三段聚合，待第三段单体转化率至少达到95％后，继续在反应釜内熟化20min；随后利用二乙烯基苯对聚合物活性分子链进行偶联，得到臂数为10的等臂长星形分子；最终得到分子结构为[S-(A_x-B_y)_n]_m-R的星形嵌段共聚物；随后将混合胶液泵入氢化釜，在加氢催化剂茂钛化合物存在下，利用氢气对混合物进行氢化，氢化反应温度为80℃，压力为0.8MPa，时间为60min；最后对产物进行凝聚和干燥得到热塑性弹性体成品。First, a solvent of n-hexane (water content: 28 ppm) and an activator were added to the polymerization vessel, and the temperature was raised to 50 ° C; then α-methylstyrene (40% by weight of the total monomer) was fed into the polymerization vessel and metered. A good catalyst, n-butyllithium, is added for the first stage of polymerization. When the monomer conversion rate is at least 95%, 2,6-di-tert-butyl-4-methylphenol is added to the active species of 50% of the active species. Inactivation, adding a mixture of isoprene/styrene (the relative weight content of styrene is 33.3% of the mixture) for the second stage polymerization, and mixing the monomers in the second stage polymerization into 5 batches (the weight of each batch) Equally) added to the polymerization vessel for reaction. When the conversion rate of each stage reaches at least 95%, the next batch of mixed monomers is added to carry out the reaction until all the mixed monomers are completely reacted; the second stage polymerization is completed. After that, α-methyl styrene (20% of the total weight of the monomer) is sent to the polymerization vessel for the third stage polymerization, and after the third stage monomer conversion rate reaches at least 95%, the aging is continued in the reactor. 20 min; subsequent use of divinylbenzene for polymer active molecular chains Joint, to give an equal number of arms 10 of the star molecule arms length; molecular structure finally obtained _{[S- (A x -B y)} n] _m -R a star block copolymers; glue is then pumped into the mixing In the hydrogenation reactor, the mixture was hydrogenated in the presence of a hydrogenation catalyst titanocene compound using hydrogen gas at a temperature of 80 ° C and a pressure of 0.8 MPa for 60 minutes. Finally, the product was coagulated and dried to obtain a finished thermoplastic elastomer.

对比例1Comparative example 1

相比于实施例1，对比例1除了没有第一段聚合中利用部分灭活而得到单分散无规聚苯乙烯的过程外，其它均与实施例1完全相同。Comparative Example 1 was identical to Example 1 except that there was no process in which the first stage polymerization was partially inactivated to obtain monodisperse atactic polystyrene.

对比例2Comparative example 2

相比于实施例2，对比例2除了没有第一段聚合中利用部分灭活而得到单分散无规聚苯乙烯的过程外，其它均与实施例2完全相同。Comparative Example 2 was identical to Example 2 except that there was no process for obtaining monodisperse atactic polystyrene by partial inactivation in the first stage polymerization.

对比例3Comparative example 3

相比于实施例3，对比例3除了没有第一段聚合中利用部分灭活而得到单分散无规聚苯乙烯的过程外，其它均与实施例3完全相同。In Comparative Example 3, Comparative Example 3 was identical to Example 3 except that there was no process in which the first stage polymerization was partially inactivated to obtain monodisperse atactic polystyrene.

利用本发明实施例1、2和3制备的微相结构特殊的氢化苯乙烯类热塑性弹性体对比对比例1、2和3，以考察本发明的有益效果。结果见表1。 The hydrogenated styrene-based thermoplastic elastomers having the microphase structure prepared in Examples 1, 2 and 3 of the present invention were compared with Comparative Examples 1, 2 and 3 to examine the advantageous effects of the present invention. The results are shown in Table 1.

表1Table 1

对比例4Comparative example 4

将对比例2中直接合成的干态新型氢化嵌段共聚物产物直接与干态单分散聚苯乙烯进行共混，利用双螺杆挤出机，加工温度为170-200℃。单分散聚苯乙烯数均分子量为20000g/mol，分子量分布为1.02。单分散聚苯乙烯占整体聚合物的重量含量与实施例1中相同。The dry new hydrogenated block copolymer product directly synthesized in Comparative Example 2 was directly blended with dry monodisperse polystyrene using a twin-screw extruder at a processing temperature of 170-200 °C. The monodisperse polystyrene has a number average molecular weight of 20,000 g/mol and a molecular weight distribution of 1.02. The monodisperse polystyrene accounts for the same weight content as the overall polymer as in Example 1.

对比例5Comparative example 5

将对比例2中直接合成的干态新型氢化嵌段共聚物产物直接与干态单分散聚苯乙烯同时利用环己烷(含水量22ppm)进行溶解均匀后，再搅拌5-10min，然后将共混溶液进行凝聚和干燥。单分散聚苯乙烯数均分子量为20000g/mol，分子量分布为1.01。单分散聚苯乙烯占整体聚合物的重量含量与实施例1中相同。The dry new hydrogenated block copolymer product directly synthesized in Comparative Example 2 was directly dissolved with dry monodisperse polystyrene using cyclohexane (water content 22 ppm), and then stirred for 5-10 min, and then The mixed solution is coagulated and dried. The monodisperse polystyrene had a number average molecular weight of 20,000 g/mol and a molecular weight distribution of 1.01. The monodisperse polystyrene accounts for the same weight content as the overall polymer as in Example 1.

对比例6Comparative example 6

将对比例2中直接合成的干态新型氢化嵌段共聚物产物产物直接与自由基聚合聚苯乙烯进行共混(市售通用级)，利用双螺杆挤出机，加工温度为170-200℃。自由基聚合聚苯乙烯数均分子量为120000g/mol，分子量分布为3.02。自由基聚合聚苯乙烯占整体聚合物的重量含量与实施例1中相同。The dry new hydrogenated block copolymer product product directly synthesized in Comparative Example 2 was directly blended with free-radically polymerized polystyrene (commercially available general grade), and the processing temperature was 170-200 ° C using a twin-screw extruder. . The radically polymerized polystyrene had a number average molecular weight of 120,000 g/mol and a molecular weight distribution of 3.02. The radically polymerized polystyrene accounts for the same weight content as the overall polymer as in Example 1.

利用本发明实施例1制备的微相结构特殊的氢化苯乙烯类热塑性弹性体对比对比例4、5和6，以考察本发明聚合工艺的有益效果。结果见表2。 The hydrogenated styrene-based thermoplastic elastomers of the microphase structure prepared in Example 1 of the present invention were compared with Comparative Examples 4, 5 and 6, to examine the advantageous effects of the polymerization process of the present invention. The results are shown in Table 2.

表2Table 2

Claims (19)

1. 一种氢化苯乙烯类热塑性弹性体，基于热塑性弹性体的总重量计，包含以下组分：A hydrogenated styrenic thermoplastic elastomer comprising the following components, based on the total weight of the thermoplastic elastomer:

   1)55-92％的氢化苯乙烯类-丁二烯类嵌段共聚物，其具有如下结构式：1) 55-92% of a hydrogenated styrene-butadiene block copolymer having the following structural formula:

   S¹ _p-D-S² _q    (I)S ¹ _p -DS ² _q (I)

   其中：among them:

   S¹和S²独立地为苯乙烯类单体聚合嵌段，S¹和S²重量分别占所述嵌段共聚物总重量的8.0-20.0％；S ¹ and S ^{2 are} independently a styrene monomer polymer block, and the weights of S ¹ and S ² are respectively 8.0 to 20.0% by weight of the total weight of the block copolymer;

   D为苯乙烯类单体与氢化共轭二烯类单体的共聚嵌段；D is a copolymer block of a styrene monomer and a hydrogenated conjugated diene monomer;

   p和q各自独立地为0或1，但不能同时为0；p and q are each independently 0 or 1, but not simultaneously 0;

   S¹、S²和D中的苯乙烯类单体单元可以相同或不同；The styrenic monomer units in S ¹ , S ² and D may be the same or different;

   其中苯乙烯类单体单元为所述氢化苯乙烯-共轭二烯类嵌段共聚物总重量的50-80重量％；Wherein the styrene monomer unit is 50 to 80% by weight based on the total weight of the hydrogenated styrene-conjugated diene block copolymer;

   2)8-45％的单分散无规聚苯乙烯。2) 8-45% monodisperse atactic polystyrene.
2. 权利要求1所述的氢化苯乙烯类热塑性弹性体，其中所述组分(1)中苯乙烯类单体为所述嵌段共聚物重量的60-75重量％。The hydrogenated styrene-based thermoplastic elastomer according to claim 1, wherein the styrenic monomer in the component (1) is from 60 to 75% by weight based on the weight of the block copolymer.
3. 权利要求1或2所述的氢化苯乙烯类热塑性弹性体，其特征在于：组分(1)氢化苯乙烯-共轭二烯类嵌段共聚物中，S¹和S²各自独立地占该嵌段共聚物重量的8.0-15.0％，优选10.0-14.0％。The hydrogenated styrene-based thermoplastic elastomer according to claim 1 or 2, wherein, in the component (1) hydrogenated styrene-conjugated diene-based block copolymer, S ¹ and S ² each independently occupy the The weight of the block copolymer is from 8.0 to 15.0%, preferably from 10.0 to 4%.
4. 权利要求1所述的氢化苯乙烯类热塑性弹性体，其中共聚嵌段D如下式所示：The hydrogenated styrene-based thermoplastic elastomer according to claim 1, wherein the copolymer block D is represented by the following formula:

   -(A_x-B_y)_n-    (II)-(A _x -B _y ) _n - (II)

   其中：among them:

   A_x为苯乙烯类单体聚合微嵌段，其中x为苯乙烯类单体单元个数， 为1-100，A _x is a styrene monomer polymerization micro block, wherein x is the number of styrene monomer units, 1-100,

   B_y为共轭二烯类单体聚合后再经氢化的氢化微嵌段，其中y为共轭二烯类单体单元个数，为1-170，B _y is a hydrogenated microblock in which a conjugated diene monomer is polymerized and then hydrogenated, wherein y is a number of conjugated diene monomer units, which is 1-170.

   n为30-1100，并且n个(A_x-B_y)中每个的氢化共轭二烯烃与苯乙烯类单体的种类和比例可以彼此相同或不同。n is 30-1100, and the kind and ratio of the hydrogenated conjugated diene and the styrene monomer of each of n (A _x -B _y ) may be the same or different from each other.
5. 权利要求4的氢化苯乙烯类热塑性弹性体，其中组分(1)为线型分子结构，结构式为S¹-(A_x-B_y)_n-S²，其中S¹、S²、A、B、x、y和n如权利要求1和4所定义。A hydrogenated styrene-based thermoplastic elastomer according to claim 4, wherein component (1) is a linear molecular structure having the formula S ¹ -(A _x -B _y ) _n -S ² wherein S ¹ , S ² , A, B, x, y and n are as defined in claims 1 and 4.
6. 权利要求4的氢化苯乙烯类热塑性弹性体，其中组分(1)为星型分子结构，结构式为[S¹-(A_x-B_y)_n-S²]_m-R或[S¹-(A_x-B_y)_n]_m-R，其中S¹、S²、A、B、x、y和n如权利要求1和4所定义，R为偶联剂残基，m为星形分子的臂数，为选自3-55的整数，优选为选自3-40的整数，更优选为选自3-15的整数。A hydrogenated styrene-based thermoplastic elastomer according to claim 4, wherein component (1) is a star-shaped molecular structure having the formula [S ¹ -(A _x -B _y ) _n -S ² ] _m -R or [S ¹ - (A _x -B _y ) _n ] _m -R, wherein S ¹ , S ² , A, B, x, y and n are as defined in claims 1 and 4, R is a coupling agent residue, m is a star The number of arms of the molecule is an integer selected from 3 to 5, preferably an integer selected from 3 to 40, and more preferably an integer selected from 3 to 15.
7. 根据权利要求1所述的氢化苯乙烯类热塑性弹性体，其特征在于：所述热塑性弹性体的数均分子量为100000-300000g/mol，分子量分布指数为1.01-1.25。The hydrogenated styrene-based thermoplastic elastomer according to claim 1, wherein the thermoplastic elastomer has a number average molecular weight of from 100,000 to 300,000 g/mol and a molecular weight distribution index of from 1.01 to 1.25.
8. 根据权利要求1所述的氢化苯乙烯类热塑性弹性体，其中所述组分(1)氢化苯乙烯-共轭二烯类嵌段共聚物中苯乙烯类单体选自苯乙烯、α-甲基苯乙烯或其组合；共轭二烯烃单体选自丁二烯、异戊二烯或其组合。The hydrogenated styrene-based thermoplastic elastomer according to claim 1, wherein the styrene monomer in the component (1) hydrogenated styrene-conjugated diene block copolymer is selected from the group consisting of styrene and α-A. The styrene or a combination thereof; the conjugated diene monomer is selected from the group consisting of butadiene, isoprene or a combination thereof.
9. 根据权利要求4所述的氢化苯乙烯类热塑性弹性体，其中所述热塑性弹性体中氢化共轭二烯烃嵌段的氢化度为80-99.99％，优选88-99.0％。 The hydrogenated styrene-based thermoplastic elastomer according to claim 4, wherein the hydrogenated conjugated diene block in the thermoplastic elastomer has a degree of hydrogenation of from 80 to 99.99%, preferably from 88 to 99.0%.
10. 根据权利要求1所述的氢化苯乙烯类热塑性弹性体，其特征在于：所述热塑性弹性体在低于60℃具有双Tg值，根据DSC方法测定其热转变，在10K/min升温时测得低Tg值在-35℃至-10℃之间，高Tg值在10℃至30℃之间。The hydrogenated styrene-based thermoplastic elastomer according to claim 1, wherein the thermoplastic elastomer has a double Tg value at less than 60 ° C, and its thermal transition is measured according to the DSC method, and is measured at a temperature rise of 10 K/min. The low Tg value is between -35 ° C and -10 ° C and the high Tg value is between 10 ° C and 30 ° C.
11. 根据权利要求1所述的氢化苯乙烯类热塑性弹性体，其具有微相分离结构：聚苯乙烯在聚合物基体中以分散相形式存在，存在平均粒径为400-900nm大的聚苯乙烯分散相以及平均粒径为10-95nm小的聚苯乙烯分散相。The hydrogenated styrene-based thermoplastic elastomer according to claim 1, which has a microphase-separated structure: polystyrene is present as a dispersed phase in a polymer matrix, and polystyrene dispersion having an average particle diameter of 400 to 900 nm is present. The phase and the polystyrene dispersed phase having an average particle diameter of 10 to 95 nm are small.
12. 根据权利要求1所述的氢化苯乙烯类热塑性弹性体，其特征在于：组分(2)阴离子聚合单分散无规聚苯乙烯的数均分子量为20000-50000g/mol，分子量分布指数为1.01-1.20。The hydrogenated styrene-based thermoplastic elastomer according to claim 1, wherein the component (2) anionically polymerized monodisperse atactic polystyrene has a number average molecular weight of 20,000 to 50,000 g/mol and a molecular weight distribution index of 1.01. 1.20.
13. 一种氢化苯乙烯类热塑性弹性体，基于热塑性弹性体的总重量计，包含以下组分：A hydrogenated styrenic thermoplastic elastomer comprising the following components, based on the total weight of the thermoplastic elastomer:

    55-92％的氢化苯乙烯类-丁二烯类嵌段共聚物，其中苯乙烯类单体为所述氢化苯乙烯-共轭二烯类嵌段共聚物总重量的50-80重量％；55-92% of a hydrogenated styrene-butadiene block copolymer, wherein the styrenic monomer is 50-80% by weight based on the total weight of the hydrogenated styrene-conjugated diene block copolymer;

    8-45％的单分散无规聚苯乙烯；8-45% monodisperse random polystyrene;

    其中所述热塑性弹性体利用DMTA测定其动态机械性能，频率固定为1Hz，升温速率3K/min时在-30-35℃出现一个明显的内耗峰(tanδ)，内耗峰的峰值在-5-10℃，且峰值tanδ≥0.3。The thermoplastic elastomer is measured by DMTA, and the frequency is fixed at 1 Hz. When the heating rate is 3 K/min, a significant internal friction peak (tan δ) appears at -30-35 ° C, and the peak of the internal friction peak is -5-10. °C, and the peak tan δ ≥ 0.3.
14. 根据权利要求1所述的氢化苯乙烯类热塑性弹性体的制备方法，其特征在于，包括以下步骤：The method for preparing a hydrogenated styrene-based thermoplastic elastomer according to claim 1, comprising the steps of:

    (i)第一段聚合：使苯乙烯类单体在聚合釜中进行阴离子活性聚合，待单体转化率至少达到95％时，苯乙烯类单体活性种的30-65重量％被部分灭活得到所述组分2)，在该聚合釜中继续加入苯乙烯类单体使得未灭活部分进行聚合或直接进行第二段聚合； (i) First-stage polymerization: anionic living polymerization is carried out in a polymerization vessel in a styrene monomer. When the monomer conversion rate is at least 95%, 30-65% by weight of the styrene monomer active species is partially eliminated. The component 2) is obtained by living, and the styrene monomer is continuously added in the polymerization vessel so that the non-inactivated portion is polymerized or directly subjected to the second-stage polymerization;

    (ii)第二段聚合：待单体转化率至少达到95％时，向聚合釜中至少分3批加入共轭二烯烃与苯乙烯类单体的混合物进行所述第二段聚合，其中后一批次在前一批次的转化率至少达到95％时加入，每一批次的共轭二烯烃与苯乙烯类单体可以彼此相同或不同；(ii) second stage polymerization: when the monomer conversion rate is at least 95%, the second stage polymerization is carried out by adding a mixture of a conjugated diene and a styrene monomer to the polymerization tank in at least three batches, wherein One batch is added when the conversion rate of the previous batch is at least 95%, and each batch of the conjugated diene and the styrene monomer may be the same or different from each other;

    (iii)任选的第三段聚合：向聚合釜中加入苯乙烯类单体进行第三段聚合；(iii) optional third stage polymerization: adding a styrenic monomer to the polymerization vessel for the third stage polymerization;

    (iv)熟化：待第二段聚合或者在存在第三段聚合时待第三段聚合中单体转化率至少达到95％后，继续在反应釜内熟化，得到线型聚合物；(iv) aging: after the second stage polymerization or in the presence of the third stage polymerization, after the monomer conversion rate in the third stage polymerization reaches at least 95%, the aging is continued in the reactor to obtain a linear polymer;

    (v)任选的偶联：向聚合釜中加入偶联剂使反应产物偶联，获得星型聚合物；(v) optional coupling: a coupling agent is added to the polymerization vessel to couple the reaction product to obtain a star polymer;

    (vi)将步骤(iv)或(v)中得到的聚苯乙烯胶液转入氢化釜、灭活，并在加氢催化剂存在下对混合物进行氢化。(vi) The polystyrene gum obtained in the step (iv) or (v) is transferred to a hydrogenation vessel, inactivated, and the mixture is hydrogenated in the presence of a hydrogenation catalyst.
15. 根据权利要求14所述的制备方法，其中所述第二段聚合期间单体的混合物分3-60批加入，优选分5-55批加入，更优选分8-40批加入。The process according to claim 14, wherein the mixture of monomers during the second stage of polymerization is added in a batch of from 3 to 60, preferably in 5 to 55 batches, more preferably in 8 to 8 batches.
16. 根据权利要求14所述的氢化苯乙烯类热塑性弹性体的制备方法，其特征在于：新型氢化苯乙烯-共轭二烯类嵌段共聚物的阴离子溶液聚合中，第二段聚合的混合单体中，苯乙烯类单体重量百分含量为20.0-64.0％，优选30.0-60.0％。The method for producing a hydrogenated styrene-based thermoplastic elastomer according to claim 14, wherein in the anionic solution polymerization of the novel hydrogenated styrene-conjugated diene block copolymer, the second stage polymerized mixed monomer The styrene monomer is present in an amount of from 20.0 to 64.0% by weight, preferably from 30.0 to 60.0% by weight.
17. 根据权利要求14或15所述的氢化苯乙烯类热塑性弹性体的制备方法，其中，第二段聚合的混合单体分批加入进行聚合时，每一批的重量相等。The method for producing a hydrogenated styrene-based thermoplastic elastomer according to claim 14 or 15, wherein the second-stage polymerized mixed monomers are added in portions to carry out polymerization, and the weight of each batch is equal.
18. 根据权利要求14所述的氢化苯乙烯类热塑性弹性体的制备方法，其中在所述第一段聚合中，部分灭活时采用的灭活剂为2，6-二叔丁 基-4-甲基苯酚。The method for producing a hydrogenated styrene-based thermoplastic elastomer according to claim 14, wherein in the first-stage polymerization, the inactivating agent used in the partial inactivation is 2,6-di-tert-butyl Base 4-methylphenol.
19. 一种氢化苯乙烯类热塑性弹性体，由权利要求14-18任一项所述的方法制备，具有微相分离结构：聚苯乙烯在聚合物基体中以分散相形式存在，存在平均粒径为400-900nm大的聚苯乙烯分散相以及平均粒径为10-95nm小的聚苯乙烯分散相。 A hydrogenated styrene-based thermoplastic elastomer prepared by the method according to any one of claims 14 to 18, having a microphase-separated structure: polystyrene is present as a dispersed phase in a polymer matrix, and an average particle diameter is present A polystyrene dispersed phase of 400-900 nm in size and a polystyrene dispersed phase having an average particle diameter of 10 to 95 nm.