WO2020078421A1

WO2020078421A1 - Fluorinated cationic polymerized monomer, and synthesis and application thereof

Info

Publication number: WO2020078421A1
Application number: PCT/CN2019/111674
Authority: WO
Inventors: 邓宇飞; 邹应全
Original assignee: 北京师范大学; 湖北固润科技股份有限公司
Priority date: 2018-10-17
Filing date: 2019-10-17
Publication date: 2020-04-23
Also published as: CN111057029B; CN111057029A

Abstract

A monomer compound of formula (I) and a method for preparing the monomer. Each variable is as defined in the description. According to the present monomer, by means of a click chemistry reaction between thiol and olefin, a perfluorinated alkane chain is introduced into an oxacycloalkane monomer by a succinate linking group, so that a photo-curable material is obtained by photo-curing of the obtained monomer cation.

Description

含氟阳离子聚合单体及其合成和应用Fluorinated cationic polymerized monomer and its synthesis and application

技术领域Technical field

本发明涉及一类新型的含氟阳离子聚合单体。本发明还涉及该单体的制备方法，该单体开环聚合得到的聚合物，包含该单体的可光固化组合物和由该可光固化组合物光固化得到的光固化材料。The invention relates to a new type of fluorine-containing cationic polymerized monomer. The invention also relates to a method for preparing the monomer, a polymer obtained by ring-opening polymerization of the monomer, a photocurable composition containing the monomer, and a photocurable material obtained by photocuring the photocurable composition.

背景技术Background technique

紫外光固化技术是指在紫外光照射下，光引发剂受激发变为自由基或者阳离子，从而引发单体间聚合形成高分子聚合物的过程。与传统热固化相比，紫外光固化技术具有速度快、能耗低、环境污染小等优点，因此紫外光固化技术在涂料、粘合剂和油墨印刷等领域有着较为广泛的应用。并且，随着有机挥发组分排放的日益严格，紫外光固化技术将具有更加广泛的应用。Ultraviolet curing technology refers to the process of photoinitiators being excited to become free radicals or cations under the irradiation of ultraviolet light, thereby initiating the polymerization process between monomers to form high molecular polymers. Compared with traditional thermal curing, ultraviolet light curing technology has the advantages of fast speed, low energy consumption, and low environmental pollution. Therefore, ultraviolet light curing technology is widely used in the fields of coatings, adhesives and ink printing. And, with the increasingly strict emission of organic volatile components, ultraviolet curing technology will have more extensive applications.

与自由基光固化相比，阳离子光固化体系具有不受氧阻聚干扰、固化涂层体积收缩小、生产成本低等优点，因而受到广泛的关注。在阳离子光固化体系中，主要使用的产品是一类具有乙烯基醚双键、脂环族环氧基、环氧乙烷基、或者氧杂环丁烷基等可阳离子光固化基团的单体、低聚物。随着消费者对涂层性能要求的日益提高，对于抗沾污、抗指纹、抗腐蚀以及抗刮蹭涂层的需求越来越大。目前能够满足以上要求的含氟光固化阳离子单体的种类比较少，需要开发更多类型的可阳离子光固化的含氟单体。Compared with free radical photo-curing, cationic photo-curing system has the advantages of not being interfered by oxygen polymerization inhibition, small volume shrinkage of cured coating, low production cost and so on, so it has received extensive attention. In the cationic photocuring system, the main product used is a type of monomer with vinyl ether double bond, alicyclic epoxy group, ethylene oxide group, or oxetane group and other cationic photocurable groups. Body, oligomer. As consumers increasingly demand coating performance, there is an increasing demand for anti-smudge, anti-fingerprint, anti-corrosion and anti-scratch coatings. At present, there are relatively few types of fluorinated photo-curable cationic monomers that can meet the above requirements, and more types of cation photo-curable fluorinated monomers need to be developed.

发明内容Summary of the invention

鉴于现有技术的上述状况，本发明的发明人在氧杂环烷烃类可阳离子聚合单体方面进行了广泛而又深入的研究，以期发现一类新型的可阳离子光固化含氟单体，该单体合成过程高效、简单，并且聚合之后得到的光固化薄膜表面能低，疏水疏油性能良好，抗油性沾污、抗指纹、抗化学品腐蚀、耐候性和抗老化能力强。本发明人发现，通过硫醇与烯烃之间的点击化学反应可以将基本上全氟化的链烷烃引入到氧杂环烷烃类单体中，可以快速、高产率合成含氟阳离子光固化单体，而且将基本上全氟化的烷烃链借助于丁二酸酯连接基引入到氧杂环烷烃类单体中，使得由所得单体阳离子光固化得到的光固化薄膜表面硬度高，表面能低，疏水疏油性能良好，尤其是抗油性沾污非常好。In view of the above-mentioned situation in the prior art, the inventors of the present invention have conducted extensive and in-depth research on the oxoalkane cationic polymerizable monomers with a view to discovering a new class of cationically photocurable fluorine-containing monomers, which The monomer synthesis process is efficient and simple, and the surface energy of the light-cured film obtained after polymerization is low, the hydrophobic and oleophobic properties are good, the oil stain resistance, fingerprint resistance, chemical corrosion resistance, weather resistance and aging resistance are strong. The present inventors found that the click chemical reaction between thiols and olefins can introduce substantially perfluorinated paraffins into oxacycloalkane monomers, and can synthesize fluorine-containing cationic photocurable monomers quickly and in high yields In addition, the substantially perfluorinated alkane chain is introduced into the oxacycloalkane monomer by means of a succinate linker, so that the surface of the photocured film obtained by the photocuring of the resulting monomer has high hardness and low surface energy , Good hydrophobic and oleophobic properties, especially good resistance to oil stains.

因此，本发明的一个目的是提供一类新型含氟可阳离子光固化单体，该单体不仅含有可阳离子光固化的氧杂环烷基基团(例如环氧乙烷基团和氧杂环丁烷基团)，而且还含有基本上全氟化的烷基。该单体可通过硫醇与烯烃之间的点击化学反应以高产率、快速合成，而且将基本上全氟化的烷烃链借助于丁二酸酯连接基引入到氧杂环烷烃类单体中，使得由所得单体阳离子光固化得到的光固化薄膜表面硬度高，表面能低，疏水疏油性能优良，尤其是抗油性沾污非常好。Therefore, an object of the present invention is to provide a new class of fluorine-containing cationic photocurable monomers, which not only contain cationic photocurable oxetanyl groups (such as ethylene oxide groups and oxetanes Butane groups), but also contains substantially perfluorinated alkyl groups. The monomer can be synthesized in a high yield and quickly by a click chemical reaction between thiol and olefin, and the substantially perfluorinated alkane chain is introduced into the oxetane monomer by means of a succinate linker It makes the photocured film obtained by the photocationic curing of the obtained monomer have high surface hardness, low surface energy, excellent hydrophobic and oleophobic properties, especially good resistance to oil stains.

本发明的另一目的是提供制备本发明含氟可阳离子光固化单体的方法。该单体可通过硫醇与烯烃之间的点击化学反应进行，因此反应快速、产率高。Another object of the present invention is to provide a method for preparing the fluorine-containing cationic photocurable monomer of the present invention. The monomer can be carried out by the click chemical reaction between thiol and olefin, so the reaction is fast and the yield is high.

本发明的再一个目的是提供由本发明含氟可阳离子光固化单体开环聚合得到的聚合物。该聚合物固化成膜的表面硬度高，表面能低，疏水疏油性能优良，尤其是抗油性沾污非常好。Another object of the present invention is to provide a polymer obtained by ring-opening polymerization of the fluorine-containing cation-curable monomer of the present invention. The cured film of the polymer has high surface hardness, low surface energy, excellent hydrophobic and oleophobic properties, especially good resistance to oil stains.

本发明的又一个目的是提供一种可光固化组合物，该组合物包含根据本发明的化合物或其混合物。Yet another object of the present invention is to provide a photocurable composition comprising the compound according to the present invention or a mixture thereof.

本发明的最后一个目的是提供一种光固化材料，该材料通过将包含本发明的可光固化组合物光固化而获得。The last object of the present invention is to provide a photo-curable material obtained by photo-curing the photo-curable composition containing the present invention.

实现本发明上述目的的技术方案可以概括如下：The technical solution for achieving the above object of the present invention can be summarized as follows:

1.下式(I)化合物：1. The compound of formula (I):

其中among them

Y为含有1-10个碳原子、优选2-8个碳原子的直链或支化烷基，该烷基的氢原子基本上全被氟替代，优选该烷基的氢原子的80-100％、优选90-100％被氟替代，更优选Y为含有3-8个碳原子的全氟直链或支化烷基；Y is a linear or branched alkyl group containing 1-10 carbon atoms, preferably 2-8 carbon atoms, the hydrogen atoms of the alkyl group are substantially completely replaced by fluorine, preferably 80-100 of the hydrogen atoms of the alkyl group %, Preferably 90-100%, is replaced by fluorine, and more preferably Y is a perfluoro linear or branched alkyl group containing 3-8 carbon atoms;

Z、Z’相同或不同且各自独立地为-(CH ₂) _p-，其中p为0、1、2或3； Z and Z 'are the same or different and are independently-(CH ₂ ) _p- , where p is 0, 1, 2 or 3;

W、W’相同或不同且各自独立地为-(CH ₂) _q-，其中q为0、1、2或3，前提是同环内的p和q不能同时为0； W and W 'are the same or different and are independently-(CH ₂ ) _q- , where q is 0, 1, 2 or 3, provided that p and q in the same ring cannot be 0 at the same time;

(R ₀) _m为W、O、Z与连接Z和W的碳原子一起构成的环上的m个取代基R ₀，其中m为0、1或2，和R ₀选自C ₁-C ₆烷基和羟基C ₁-C ₆烷基，其中当m为2时，两个R ₀可相同或不同； (R ₀ ) _m is m substituents R ₀ on the ring formed by W, O, Z and the carbon atoms connecting Z and W together, wherein m is 0, 1 or 2, and R _{0 is} selected from C ₁ -C ₆ alkyl and hydroxy C ₁ -C ₆ alkyl, wherein when m is 2, the two R ₀ may be the same or different;

(R ₀’) _m’为W’、O、Z’与连接Z’和W’的碳原子一起构成的环上的m’个取代基R ₀’，其中m’为0、1或2，和R ₀’选自C ₁-C ₆烷基和羟基C ₁-C ₆烷基，其中当m’为2时，两个R ₀’可相同或不同，(R ₀) _m与(R ₀’) _m’相同或不同； (R ₀ ') _m' is m 'substituents R ₀ ' on the ring formed by W ', O, Z' and the carbon atoms connecting Z 'and W', wherein m 'is 0, 1 or 2, And R ₀ 'are selected from C ₁ -C ₆ alkyl and hydroxy C ₁ -C ₆ alkyl, wherein when m' is 2, the two R ₀ 'may be the same or different, (R ₀ ) _m and (R ₀ ') _{m' is the} same or different;

n1、n1’相同或不同且各自独立地为1或2；n1, n1 'are the same or different and are independently 1 or 2;

n3为1、2、3或4；n3 is 1, 2, 3 or 4;

R ₁、R ₂、R ₁’和R ₂’各自独立地选自H、C ₁-C ₆烷基和C ₁-C ₆烷氧基，当n1为2时，两个R ₁可相同或不同，和两个R ₂可相同或不同，当n1’为2时，两个R ₁’可相同或不同，和两个R ₂’可相同或不同；以及 R ₁ , R ₂ , R ₁ 'and R ₂ ' are each independently selected from H, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy, when n1 is 2, the two R ₁ may be the same or Different, and two R ₂ may be the same or different, when n1 'is 2, two R ₁ ' may be the same or different, and two R ₂ 'may be the same or different; and

R ₅和R ₆各自独立地选自H和C ₁-C ₆烷基，其中当n3为2、3或4时，n3个R ₅可相同或不同，和n3个R ₆可相同或不同。 R ₅ and R ₆ are each independently selected from H and C ₁ -C ₆ alkyl, wherein when n 3 is 2, 3 or 4, n 3 R ₅ may be the same or different, and n 3 R ₆ may be the same or different.

2.如第1项所述的化合物，其中同环内的p和q均为1，或者同环内的p和q中之一为0，另一为1。2. The compound according to item 1, wherein p and q in the same ring are both 1, or one of p and q in the same ring is 0, and the other is 1.

3.如第1或2项所述的化合物，其中m为0或1，当m为1时，R ₀优选位于连接Z和W的碳原子上；和/或，m’为0或1，当m’为1时，R _0’优选位于连接Z’和W’的碳原子上。 3. The compound according to item 1 or 2, wherein m is 0 or 1, and when m is 1, R ₀ is preferably located on the carbon atom connecting Z and W; and / or, m ′ is 0 or 1, When m 'is 1, R _0' is preferably located on the carbon atom connecting Z 'and W'.

4.如第1-3项中任一项所述的化合物，其中n1和/或n1’为1；和/或，n3为2。4. The compound according to any one of items 1-3, wherein n1 and / or n1 'is 1; and / or, n3 is 2.

5.如第1-4项中任一项的化合物，其中5. The compound according to any one of items 1 to 4, wherein

R ₀和R ₀’相同或不同且独立地选自C ₁-C ₄烷基和羟基C ₁-C ₄烷基；和/或 R ₀ and R ₀ 'are the same or different and are independently selected from C ₁ -C ₄ alkyl and hydroxy C ₁ -C ₄ alkyl; and / or

R ₁、R ₂、R ₁’和R ₂’各自独立地选自H、C ₁-C ₄烷基和C ₁-C ₄烷氧基，优选R ₁、R ₂、R ₁’和R ₂’均为H；和/或 R ₁ , R ₂ , R ₁ ′ and R ₂ ′ are each independently selected from H, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, preferably R ₁ , R ₂ , R ₁ ′ and R ₂ 'All H; and / or

R ₅和R ₆各自独立地选自H和C ₁-C ₄烷基，优选均为H。 R ₅ and R ₆ are each independently selected from H and C ₁ -C ₄ alkyl, preferably both are H.

6.如第1-5项中任一项的化合物，其中Z与Z’相同，W与W’相同，(R ₀) _m与(R ₀’) _m’相同，n1与n1’相同，R ₁与R ₁’相同，以及R ₂与R ₂’相同。 6. The compound according to any one of items 1 to 5, wherein Z is the same as Z ', W is the same as W', (R ₀ ) _{m is the} same as (R ₀ ') _m' , n1 is the same as n1 ', R _{1 is the} same as R ₁ ', and R _{2 is the} same as R ₂ '.

7.如第1项的化合物，其为选自化合物C-1至C-12的化合物。7. The compound according to item 1, which is a compound selected from compounds C-1 to C-12.

8.一种制备如第1-7项中任一项所述的式(I)化合物的方法，包括：8. A method for preparing the compound of formula (I) according to any one of items 1-7, comprising:

1)使式(II)化合物1) The compound of formula (II)

其中X和X’相同或不同且各自独立地为卤素，优选氯或溴；Where X and X 'are the same or different and are each independently halogen, preferably chlorine or bromine;

与式(III)化合物进行酯化反应或与式(III)化合物和式(III’)化合物先后进行酯化反应，Performing an esterification reaction with a compound of formula (III) or successively performing an esterification reaction with a compound of formula (III) and a compound of formula (III ’),

其中Z、Z’、W、W’、R ₀、R ₀’、R ₁、R ₁’、R ₂、R ₂’、m、m’、n1和n1’如对式(I)化合物所定义， Where Z, Z ', W, W', R ₀ , R ₀ ', R ₁ , R ₁ ', R ₂ , R ₂ ', m, m', n1 and n1 'are as defined for the compound of formula (I) ,

得到式(IV)化合物，The compound of formula (IV) is obtained,

其中Z、Z’、W、W’、R ₀、R ₀’、R ₁、R ₁’、R ₂、R ₂’、m、m’、n1和n1’如对式(I)化合物所定义；以及 Where Z, Z ', W, W', R ₀ , R ₀ ', R ₁ , R ₁ ', R ₂ , R ₂ ', m, m', n1 and n1 'are as defined for the compound of formula (I) ;as well as

2)使式(IV)化合物与式(V)化合物反应，2) React the compound of formula (IV) with the compound of formula (V),

其中R ₅、R ₆、n3和Y如对式(I)化合物所定义， Where R ₅ , R ₆ , n3 and Y are as defined for the compound of formula (I),

得到式(I)化合物。The compound of formula (I) is obtained.

9.如第8项所述的方法，其中步骤1)中的反应在俘酸剂存在下进行，优选俘酸剂为三乙胺、苯胺、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾或其任意混合物。9. The method according to item 8, wherein the reaction in step 1) is carried out in the presence of an acid trapping agent, preferably the acid trapping agent is triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate Or any mixture thereof.

10.如第8或9项所述的方法，其中当式(II)化合物与仅仅式(III)化合物进行酯化反应时(即Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’每组各自相同时)，式(III)化合物与式(II)化合物的摩尔比为2.0-3.0，优选为2.1-2.5；当式(II)化合物与式(III)化合物和式(III’)化合物先后进行酯化反应时(即Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’这几组中至少一组不同时)，式(III)化合物和式(III’)化合物各自与式(II)化合物的摩尔比为1.0-2.0，优选为1.1-1.5；和/或，俘酸剂与式(II)化合物的摩尔比为2.0-3.0，优选为2.1-2.5；和/或，步骤1)中的反应在20-30℃的温度下进行，优选在室温下进行。 10. The method according to item 8 or 9, wherein when the compound of formula (II) and only the compound of formula (III) undergo an esterification reaction (ie, Z and Z ', W and W', R ₀ and R ₀ ' , R ₁ and R ₁ ', R ₂ and R ₂ ', m and m 'and n1 and n1' are the same in each group), the molar ratio of the compound of formula (III) to the compound of formula (II) is 2.0-3.0, Preferably it is 2.1-2.5; when the compound of formula (II) and the compound of formula (III) and the compound of formula (III ') are successively subjected to an esterification reaction (ie Z and Z', W and W ', R ₀ and R ₀ ', (At least one of R ₁ and R ₁ ', R ₂ and R ₂ ', m and m ', and n1 and n1' are different), the compound of formula (III) and the compound of formula (III ') are each different from the formula ( II) The molar ratio of the compound is 1.0-2.0, preferably 1.1-1.5; and / or, the molar ratio of the acid trapping agent to the compound of formula (II) is 2.0-3.0, preferably 2.1-2.5; and / or, step 1 ) Is carried out at a temperature of 20-30 ° C, preferably at room temperature.

11.如第8-11项中任一项所述的方法，其中步骤2)的反应按照步骤2a)进行：2a)在自由基引发剂存在下和在无氧气的条件下，使式(IV)化合物与式(V)化合物进行反应，优选的是，11. The method according to any one of items 8 to 11, wherein the reaction of step 2) is carried out according to step 2a): 2a) in the presence of a radical initiator and in the absence of oxygen, the formula (IV ) The compound reacts with the compound of formula (V), preferably,

所述自由基引发剂选自偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过氧化二苯甲酰或其任意混合物；和/或，式(IV)化合物与式(V)化合物的摩尔比为0.8-1.5，优选0.9-1.1；和/或，步骤2a)的反应在40-110℃，优选50-100℃的温度下进行。The free radical initiator is selected from azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide or any mixture thereof; and / or, formula (IV ) The molar ratio of the compound to the compound of formula (V) is 0.8-1.5, preferably 0.9-1.1; and / or the reaction of step 2a) is carried out at a temperature of 40-110 ° C, preferably 50-100 ° C.

12.如第8-11项中任一项所述的方法，其中步骤2)的反应按照步骤2b)进行：2b)使式(IV)化合物和式(V)化合物在紫外光照射下反应，优选的是，12. The method according to any one of items 8 to 11, wherein the reaction of step 2) is performed according to step 2b): 2b) The compound of formula (IV) and the compound of formula (V) are reacted under ultraviolet light irradiation, Preferably,

步骤2b)的反应在发射波段为300-600nm的紫外灯照射下进行；和/或，式(IV)化合物与式(V)化合物的摩尔比为0.8-1.5，优选0.9-1.0；和/或，步骤2b)的反应在室温下进行。The reaction of step 2b) is carried out under the irradiation of an ultraviolet lamp with an emission band of 300-600 nm; and / or, the molar ratio of the compound of formula (IV) to the compound of formula (V) is 0.8-1.5, preferably 0.9-1.0; and / or The reaction of step 2b) is carried out at room temperature.

13.一种聚合物，其通过将如第1-7项中任一项所述的式(I)化合物通过开环聚合而得到，优选通过阳离子光固化开环聚合而得到，该阳离子光固化开环聚合尤其是在光引发剂存在下进行紫外光固化而实现。13. A polymer obtained by ring-opening polymerization of the compound of formula (I) according to any one of items 1-7, preferably by cationic photo-curing ring-opening polymerization, the cationic photo-curing The ring-opening polymerization is achieved in particular by ultraviolet curing in the presence of a photoinitiator.

14.一种可光固化组合物，包含如第1-7项中任一项所述的式(I)化合物作为聚合单体。14. A photocurable composition comprising the compound of formula (I) according to any one of items 1 to 7 as a polymerizable monomer.

15.一种光固化材料，该材料通过将根据第14项的可光固化组合物光固化而获得。15. A photocurable material obtained by photocuring the photocurable composition according to item 14.

具体实施方式detailed description

根据本发明的一个方面，提供了一种下式(I)化合物：According to one aspect of the invention, there is provided a compound of formula (I):

其中among them

Y为含有1-10个碳原子的直链或支化烷基，该烷基的氢原子基本上全被氟替代；Y is a linear or branched alkyl group containing 1-10 carbon atoms, the hydrogen atoms of which are substantially completely replaced by fluorine;

n3为1、2、3或4；n3 is 1, 2, 3 or 4;

R ₁、R ₂、R ₁’和R ₂’各自独立地选自H、C ₁-C ₆烷基和C ₁-C ₆烷氧基，当n1为2 时，两个R ₁可相同或不同，和两个R ₂可相同或不同，当n1’为2时，两个R ₁’可相同或不同，和两个R ₂’可相同或不同；以及 R ₁ , R ₂ , R ₁ ′ and R ₂ ′ are each independently selected from H, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy, when n1 is 2, the two R ₁ may be the same or Different, and two R ₂ may be the same or different, when n1 'is 2, two R ₁ ' may be the same or different, and two R ₂ 'may be the same or different; and

R ₅和R ₆各自独立地选自H和C ₁-C ₆烷基，其中当n3为2、3或4时，n3个R ₅ R ₅ and R ₆ are each independently selected from H and C ₁ -C ₆ alkyl, wherein when n 3 is 2, 3 or 4, n 3 R ₅

可相同或不同，和n3个R ₆可相同或不同。 May be the same or different, and n3 R ₆ may be the same or different.

在本发明化合物中，Y为含有1-10个碳原子的基本上全氟化的直链或支化烷基，优选为含有2-8个碳原子的基本上全氟化的直链或支化烷基，更优选为含有3-8个碳原子的全氟直链或支化烷基。在本发明中，“基本上全氟化的直链或支化烷基”指的是该直链或支化烷基的所有氢原子中至少80％被氟替代，优选该直链或支化烷基的氢原子的80-100％、更优选90-100％被氟替代，尤其是该直链或支化烷基的所有氢原子被氟替代，即Y为全氟化烷基。作为Y的实例，可以提及三氟甲基、四氟乙基、五氟乙基、七氟丙基、1-三氟甲基四氟乙基、九氟丁基、十一氟戊基和十三氟己基。In the compounds of the present invention, Y is a substantially perfluorinated linear or branched alkyl group containing 1-10 carbon atoms, preferably a substantially perfluorinated linear or branched chain containing 2-8 carbon atoms The alkylated alkyl group is more preferably a perfluoro linear or branched alkyl group containing 3 to 8 carbon atoms. In the present invention, "substantially perfluorinated linear or branched alkyl group" means that at least 80% of all hydrogen atoms of the linear or branched alkyl group are replaced by fluorine, preferably the linear or branched alkyl group 80-100%, more preferably 90-100% of the hydrogen atoms of the alkyl group are replaced by fluorine, especially all the hydrogen atoms of the linear or branched alkyl group are replaced by fluorine, ie Y is a perfluorinated alkyl group. As examples of Y, mention may be made of trifluoromethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, 1-trifluoromethyltetrafluoroethyl, nonafluorobutyl, undecafluoropentyl and Thirteen fluorohexyl.

Z和W为本发明化合物中氧杂环烷烃结构部分的组成部分,Z’和W’为本发明化合物中另一氧杂环烷烃结构部分的组成部分。Z、Z’相同或不同且各自独立地为-(CH ₂) _p-，其中p为0、1、2或3。W、W’相同或不同且各自独立地为-(CH ₂) _q-，其中q为0、1、2或3，前提是同环内的p和q不能同时为0。优选的是，同环内的p和q均为1，或者同环内的p和q中之一为0，另一为1。也就是说，优选的是，本发明化合物中的氧杂环烷烃结构部分为氧杂环丁烷或环氧乙烷环。 Z and W are components of the oxacycloalkane structural part in the compound of the present invention, and Z 'and W' are components of another oxacycloalkane structural part in the compound of the present invention. Z and Z 'are the same or different and are each independently-(CH ₂ ) _p- , where p is 0, 1, 2 or 3. W and W 'are the same or different and are independently-(CH ₂ ) _q- , where q is 0, 1, 2 or 3, provided that p and q in the same ring cannot be 0 at the same time. Preferably, p and q in the same ring are both 1, or one of p and q in the same ring is 0, and the other is 1. That is, it is preferable that the oxetane structural part in the compound of the present invention is an oxetane or an ethylene oxide ring.

(R ₀) _m为W、O、Z与连接Z和W的碳原子一起构成的环上的m个取代基R ₀，其中m为0、1或2，和R ₀选自C ₁-C ₆烷基和羟基C ₁-C ₆烷基，其中当m为2时，两个R ₀可相同或不同。优选的是，m为0或1。当m为1时，R ₀有利地位于连接Z和W的碳原子上。R ₀优选选自C ₁-C ₄烷基和羟基C ₁-C ₄烷基，例如甲基、乙基、丙基、丁基、羟甲基、羟乙基、羟丙基和羟丁基。 (R ₀ ) _m is m substituents R ₀ on the ring formed by W, O, Z and the carbon atoms connecting Z and W together, wherein m is 0, 1 or 2, and R _{0 is} selected from C ₁ -C ₆ alkyl and hydroxy C ₁ -C ₆ alkyl, wherein when m is 2, the two R ₀ may be the same or different. Preferably, m is 0 or 1. When m is 1, R _{0 is} advantageously located on the carbon atom connecting Z and W. R ₀ is preferably selected from C ₁ -C ₄ alkyl and hydroxy C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl, butyl, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl .

(R ₀’) _m’为W’、O、Z’与连接Z’和W’的碳原子一起构成的环上的m’个取代基R ₀’，其中m’为0、1或2，和R ₀’选自C ₁-C ₆烷基和羟基C ₁-C ₆烷基，其中当m’为2时，两个R ₀’可相同或不同，(R ₀) _m与(R ₀’) _m’相同或不同。优选的是，m’为0或1。当m’为1时，R ₀’有利地位于连接Z’和W’的碳原子上。R ₀’优选选自C ₁-C ₄烷基和羟基C ₁-C ₄烷基，例如甲基、乙基、丙基、丁基、羟甲基、羟乙基、羟丙基和羟丁基。 (R ₀ ') _m' is m 'substituents R ₀ ' on the ring formed by W ', O, Z' and the carbon atoms connecting Z 'and W', wherein m 'is 0, 1 or 2, And R ₀ 'are selected from C ₁ -C ₆ alkyl and hydroxy C ₁ -C ₆ alkyl, wherein when m' is 2, the two R ₀ 'may be the same or different, (R ₀ ) _m and (R ₀ ') _{m' is the} same or different. Preferably, m 'is 0 or 1. When m 'is 1, R ₀ ' is advantageously located on the carbon atom connecting Z 'and W'. R ₀ ′ is preferably selected from C ₁ -C ₄ alkyl and hydroxy C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl, butyl, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutane base.

特别优选的是，(R ₀) _m与(R ₀’) _m’相同，即，取代基R ₀与R ₀’相同且其取代位置相同，并且取代基的数量m和m’也相同。 It is particularly preferred that (R ₀ ) _{m is the} same as (R ₀ ') _m' , that is, the substituents R ₀ and R ₀ 'are the same and their substitution positions are the same, and the number of substituents m and m' are also the same.

在本发明中，n1、n1’相同或不同且各自独立地为1或2，优选均为1。R ₁、R ₂、R ₁’和R ₂’各自独立地选自H、C ₁-C ₆烷基和C ₁-C ₆烷氧基，优选各自独立地选自H、C ₁-C ₄烷基和C ₁-C ₄烷氧基，例如甲基、乙基、丙基、丁基、甲氧基、乙氧基、丙氧基和丁氧基。当n1为2时，两个R ₁可相同或不同，和两个R ₂可相同或不同。当n1’为2时，两个R ₁’可相同或不同，和两个R ₂’可相同或不同。特别优选R ₁、R ₂、R ₁’和R ₂’均为H。 In the present invention, n1 and n1 'are the same or different and are each independently 1 or 2, preferably 1 both. R ₁ , R ₂ , R ₁ ′ and R ₂ ′ are each independently selected from H, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy, preferably each independently selected from H, C ₁ -C ₄ Alkyl and C ₁ -C ₄ alkoxy, such as methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy and butoxy. When n1 is 2, two R ₁ may be the same or different, and two R ₂ may be the same or different. When n1 'is 2, two R _1' may be the same or different, and two R ₂ 'may be the same or different. It is particularly preferred that R ₁ , R ₂ , R ₁ ′ and R ₂ ′ are all H.

在本发明中，n3为1、2、3或4，优选为2。R ₅和R ₆各自独立地选自H和C ₁-C ₆烷基，优选各自独立地选自H和C ₁-C ₄烷基，例如甲基、乙基、丙基、丁基。当n3为2、3或4时，n3个R ₅可相同或不同，和n3个R ₆可相同或不同。特别优选R ₅和R ₆均为H。 In the present invention, n3 is 1, 2, 3 or 4, preferably 2. R ₅ and R ₆ are each independently selected from H and C ₁ -C ₆ alkyl, preferably each independently selected from H and C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl, butyl. When n3 is 2, 3 or 4, n3 R ₅ may be the same or different, and n3 R ₆ may be the same or different. It is particularly preferred that both R ₅ and R ₆ are H.

在本发明的一个尤其优选的实施方案中，Z与Z’相同，W与W’相同，(R ₀) _m与(R ₀’) _m’相同，n1与n1’相同，R ₁与R ₁’相同，以及R ₂与R ₂’相同。 In a particularly preferred embodiment of the present invention, Z is the same as Z ', W is the same as W', (R ₀ ) _{m is the} same as (R ₀ ') _m' , n1 is the same as n1 ', R ₁ is R ₁ 'Same, and R ₂ and R ₂ ' are the same.

本发明化合物中含有基本上全氟化的烷基。氟是电负性最强的元素，C-F键短，使得键角变小，氟原子沿碳链呈螺旋分布，故整个碳链的极性基本相互抵消，因此整个分子极性低，由此制备的涂层表面能低。这种特殊的结构使整个分子十分僵硬，分子转动势垒很大，因此具有很好的耐候性和耐化学品性。由于含氟物质具有极强的迁移性，会迁移到界面处，所以添加极少量的含氟化合物就会大大降低涂层的表面张力。另外，由于C-F键键能高难断裂，在高温、湿度大的复杂环境内也能保护涂层防止被腐蚀氧化。这类单体在印刷版材成像材料，抗污耐腐蚀光固化涂料，光固化油墨，光致抗蚀剂以及抗沾污或无指印涂层中有很好的应用前景。与一般意义上的光固化聚合物相比，含氟光固化聚合物具有疏水性好、表面张力低等特点，解决了材料在应用过程中令人头痛的粘连、铺展性不好等问题。其较小的附着力和良好的铺展性在微电子技术、精密光学仪器制造、精密印刷、航空航天、海洋防污、生物化学等领域具有广阔的应用前景。例如：印刷过程中加入含有氟、硅等元素的单体能增强固化薄膜表面的铺展性，表面疏水性也增强，便于油墨更好地铺展；纳米压印过程中，含氟、硅的材料由于其较低的表面能可作为良好的脱模材料，从而有效解决光刻胶粘度大不易与模具分离的问题。The compounds of the present invention contain substantially perfluorinated alkyl groups. Fluorine is the most electronegative element. The CF bond is short, which makes the bond angle smaller. The fluorine atoms are distributed spirally along the carbon chain. Therefore, the polarity of the entire carbon chain basically cancels each other, so the entire molecule has a low polarity. The surface energy of the coating is low. This special structure makes the entire molecule very stiff, and the molecular rotation barrier is very large, so it has good weather resistance and chemical resistance. Since the fluorine-containing substance has extremely strong mobility and will migrate to the interface, adding a very small amount of fluorine-containing compound will greatly reduce the surface tension of the coating. In addition, because the C-F bond can be difficult to break, it can also protect the coating from corrosion and oxidation in complex environments with high temperatures and high humidity. Such monomers have good application prospects in printing plate imaging materials, anti-fouling and corrosion-resistant photo-curing coatings, photo-curing inks, photoresists, and anti-fouling or fingerprint-free coatings. Compared with the general photo-curing polymer, the fluorine-containing photo-curing polymer has the characteristics of good hydrophobicity and low surface tension, which solves the problems such as sticky adhesion and poor spreadability of the material in the application process. Its small adhesion and good spreadability have broad application prospects in microelectronics technology, precision optical instrument manufacturing, precision printing, aerospace, marine antifouling, biochemistry and other fields. For example: adding monomers containing fluorine, silicon and other elements during the printing process can enhance the spreadability of the cured film surface, and the surface hydrophobicity is also enhanced to facilitate better ink spreading; during the nano-imprinting process, materials containing fluorine and silicon Its lower surface energy can be used as a good mold release material, thereby effectively solving the problem that the viscosity of the photoresist is not easy to separate from the mold.

本发明化合物通过丁二酸酯连接基团将可阳离子光固化氧杂环烷基与基本上全氟化烷基连接。基本上全氟化的烷基在固化体系中具有向界面处迁移的能力，不仅在涂层表面形成全氟化的覆盖层，有效地降低整个涂层的表面能，还能将丁二酸酯连接的可阳离子光固化氧杂环烷基同时带到表面，增加了涂层表面的交联密度。丁二酸酯结构并未影响氧杂环烷基的阳离子聚合，在阳离子引发剂的作用下，紫外光引发发生阳离子聚合。最终聚合度接近百分之百，具有很好的固化速率和固化效率。此外，本发明的发明人发现，由于涂层表面丁二酸酯所连接氧杂环烷基的聚合导致涂层表面交联密度增加具有提高涂层硬度的效果，能够使涂层具有非常好的耐磨性能和抗油性沾污性。The compound of the present invention connects the cationic photocurable oxetanyl group to the substantially perfluorinated alkyl group through a succinate linking group. Basically, the perfluorinated alkyl group has the ability to migrate to the interface in the curing system. Not only does it form a perfluorinated coating on the surface of the coating, which effectively reduces the surface energy of the entire coating, but also reduces the succinate The attached cationic photocurable oxetanyl group is simultaneously brought to the surface, increasing the crosslink density of the coating surface. The succinate structure does not affect the cationic polymerization of oxetanyl groups. Under the action of a cationic initiator, UV light initiates cationic polymerization. The final degree of polymerization is close to 100%, with a good curing rate and curing efficiency. In addition, the inventors of the present invention found that the increase in the cross-link density of the coating surface due to the polymerization of the oxetanyl group attached to the succinate on the surface of the coating has the effect of increasing the hardness of the coating, and can make the coating have a very good Wear resistance and oil stain resistance.

本发明的一个优选实施方案中，本发明化合物选自下组：In a preferred embodiment of the present invention, the compound of the present invention is selected from the group consisting of:

本发明式(I)化合物的一个重要特点在于，可以通过硫醇化合物与烯烃化合物之间的点击化学反应而高产率、快速合成。An important feature of the compound of formula (I) of the present invention is that it can be synthesized in a high yield and quickly by a click chemical reaction between a thiol compound and an olefin compound.

因此，根据本发明的第二方面，提供了一种制备本发明式(I)化合物的方法，该方法包括：Therefore, according to the second aspect of the present invention, there is provided a method for preparing the compound of formula (I) of the present invention, the method comprising:

1)使式(II)化合物1) The compound of formula (II)

得到式(IV)化合物，The compound of formula (IV) is obtained,

得到式(I)化合物。The compound of formula (I) is obtained.

在本发明方法中，首先使式(II)化合物与式(III)化合物通过酯化反应获得式(IV)化合物，或者使式(II)化合物与式(III)化合物和式(III’)化合物先后通过酯化反应获得式(IV)化合物，然后由式(IV)化合物和式(V)化合物反应获得式(I)化合物。本领域技术人员应当理解，当所要制备的式(I)化合物中，Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’每组各自相同时，在步骤1)中，使式(II)化合物与式(III)化合物反应即可；只有当Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’这几组中至少一种不同时，则在步骤1)中使式(II)化合物与式(III)化合物和式(III’)化合物先后进行酯化反应。对于先后进行酯化反应的情形，使式(II)化合物与式(III)化合物和式(III’)化合物中的一种先反应，将两个酰基卤中的一个反应掉生成相应的单酯，然后再与式(III)化合物和式(III’)化合物中的另一种反应，将剩余的酰基卤反应掉生成相应的二酯。 In the method of the present invention, the compound of formula (II) and the compound of formula (III) are first subjected to an esterification reaction to obtain the compound of formula (IV), or the compound of formula (II) and the compound of formula (III) and the compound of formula (III ') The compound of formula (IV) is obtained through an esterification reaction successively, and then the compound of formula (I) is obtained from the reaction of the compound of formula (IV) and the compound of formula (V). Those skilled in the art should understand that in the compound of formula (I) to be prepared, Z and Z ′, W and W ′, R ₀ and R ₀ ′, R ₁ and R ₁ ′, R ₂ and R ₂ ′, m When each group is the same as m 'and n1 and n1', in step 1), the compound of formula (II) and the compound of formula (III) can be reacted; only when Z and Z ', W and W', R ₀ When it is different from at least one of the groups R ₀ ', R ₁ and R ₁ ', R ₂ and R ₂ ', m and m' and n1 and n1 ', the compound of formula (II) is used in step 1) The compound of formula (III) and the compound of formula (III ') are successively subjected to an esterification reaction. In the case of successive esterification reactions, the compound of formula (II) is reacted with one of the compound of formula (III) and the compound of formula (III ') first, and one of the two acid halides is reacted to form the corresponding monoester , And then with the compound of formula (III) and another compound of formula (III '), the remaining acid halide is reacted to form the corresponding diester.

步骤1)中的反应为酯化反应。式(II)化合物为酰卤化合物，式(III)化合物和式(III’)化合物为醇化合物，因此步骤1)中的酯化反应为典型的酰卤化合物与醇化合物之间的酯化反应。式(II)化合物可以直接市购获得或者通过常规的反应制得。为了制得式(II)化合物，可以使其中X为羟基的式(II)化合物(即丁烯二酸，例如富马酸和马来酸)在无水的条件下与酰卤化试剂，尤其是酰氯化试剂反应，从而获得式(II)的酰卤化合物。作为这里的酰卤化试剂，可以使用氯化亚砜(二氯亚砜)、三氯氧磷、五氯化磷、草酰氯或者它们的任意混合物。由于酰卤化试剂易与水反应，从而降低反应效率，因此该反应需要在无水条件下进行，生成的酰卤化合物(II)之后与式(III)化合物和任选的式(III’)化合物的反应也需要在无水条件下反应，因为生成的酰卤化合物也易与水反应而降低反应产率。为此，为了实现反应方案的无水条件，各反应原料需要进行脱水处理。通常的做法可以是向原料中加入分子筛如3A分子筛，静置放置一段时间比如24h吸水，然后滤除分子筛。如果反应需要非水溶剂，则该溶剂通常也需要在反应前进行脱水处理，通常的做法包括向该溶剂中加入钠砂，二苯甲酮作为指示剂，加热回流即蒸即用。另外，使用的反应容器如玻璃容器也需要在反应前于100-110℃烘至少半小时再使用。The reaction in step 1) is an esterification reaction. The compound of formula (II) is an acid halide compound, the compound of formula (III) and the compound of formula (III ') are alcohol compounds, so the esterification reaction in step 1) is a typical esterification reaction between an acid halide compound and an alcohol compound . The compound of formula (II) can be obtained directly from the market or prepared by conventional reaction. In order to prepare the compound of formula (II), the compound of formula (II) in which X is hydroxy (ie, butenedioic acid, such as fumaric acid and maleic acid) can be reacted with an acid halogenating reagent under anhydrous conditions, especially The acid chlorination reagent reacts to obtain the acid halide compound of formula (II). As the acid halogenating agent here, sulfoxide chloride (dichlorosulfoxide), phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride, or any mixture thereof can be used. Since the acid halide reagent easily reacts with water, thereby reducing the reaction efficiency, the reaction needs to be carried out under anhydrous conditions. The resulting acid halide compound (II) is then combined with the compound of formula (III) and the optional compound of formula (III ') The reaction also needs to react under anhydrous conditions, because the resulting acid halide compound also easily reacts with water and reduces the reaction yield. For this reason, in order to realize the anhydrous conditions of the reaction scheme, each reaction raw material needs to be dehydrated. A common practice can be to add molecular sieves, such as 3A molecular sieves, to the raw materials for a period of time, such as 24h, to absorb water, and then filter out the molecular sieves. If a non-aqueous solvent is required for the reaction, the solvent usually needs to be dehydrated before the reaction. The usual practice includes adding sodium sand to the solvent and benzophenone as an indicator, heating and refluxing and then steaming. In addition, the reaction vessel used, such as a glass vessel, needs to be baked at 100-110 ° C for at least half an hour before the reaction.

考虑到少量酰卤化试剂仍会与空气中的水分发生反应，因此有利的是，酰卤化试剂过量使用，即酰卤化试剂相对于与之反应的丁烯二酸以2.5-10倍的摩尔比使用，优选3-5倍的摩尔比使用。例如当使用氯化亚砜或草酰氯作为酰卤化试剂时，相对于丁烯二酸，氯化亚砜或草酰氯的用量以摩尔计为3-5倍摩尔量。酰卤化试剂与丁烯二酸的反应通常需要在高温下进行，因此有利的是，丁烯二酸与酰卤化试剂在无水条件下的反应在60-90℃的温度下进行，优选在70-80℃的温度下进行。该反应的时间通常为2-10小时，优选为4-6小时。丁烯二酸与酰卤化试剂在无水条件下的反应可以在非水溶剂存在下进行。对此，可以使用的溶剂包括二氯甲烷、四氢呋喃、正己烷、石油醚、1,4-二氧六环、乙腈或其任意混合物。对于溶剂的用量，没有特别的限制，只要能将各反应物充分溶解即可。通常而言，溶剂的用量为反应物总量的2-50倍重量。Considering that a small amount of acyl halide reagent will still react with moisture in the air, it is advantageous that the acyl halide reagent is used in excess, that is, the acyl halide reagent is used at a molar ratio of 2.5-10 times relative to the butadiene acid reacted with It is preferably used in a molar ratio of 3-5 times. For example, when sulfoxide chloride or oxalyl chloride is used as the acid halogenation reagent, the amount of sulfoxide chloride or oxalyl chloride used is 3-5 times the molar amount based on moles with respect to butenedioic acid. The reaction of the acid halogenation reagent and the succinic acid usually needs to be carried out at a high temperature, so it is advantageous that the reaction of the crotonic acid and the acid halogenation reagent under anhydrous conditions is carried out at a temperature of 60-90 ° C, preferably at 70 -At a temperature of -80 ° C. The reaction time is usually 2-10 hours, preferably 4-6 hours. The reaction of crotonic acid and the acid halogenating reagent under anhydrous conditions can be carried out in the presence of a non-aqueous solvent. For this, solvents that can be used include dichloromethane, tetrahydrofuran, n-hexane, petroleum ether, 1,4-dioxane, acetonitrile, or any mixture thereof. There is no particular restriction on the amount of solvent used, as long as each reactant can be fully dissolved. Generally speaking, the amount of solvent is 2-50 times the total weight of the reactants.

丁烯二酸与酰卤化试剂反应完成之后，获得式(II)化合物。该化合物可以经彻底分离出来后再与式(III)化合物反应或与式(III)化合物和式(III’)化合物先后反应，也可通过先旋蒸后减压蒸馏除去多余的酰卤化试剂后，再引入式(III)化合物继续反应或与式(III)化合物和式(III’)化合物先后继续反应。由于式(II)化合物与式(III)化合物的反应以及式(II)化合物与式(III)化合物和式(III’)化合物的先后反应会产生酸性物质卤化氢，为了防止酸性物质所导致的副反应而降低最终的产率，步骤1)中的反应通常在俘酸剂存在下进行。作为俘酸剂，可以使用三乙胺、苯胺、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾或其任意混合物。俘酸剂的用量或总用量(式(II)化合物与式(III)化合物和式(III’)化合物先后反应的情形)通常应使得俘酸剂与式(II)化合物的摩尔比为2.0-3.0，优选为2.1-2.5。例如，当使用三乙胺或苯胺作为俘酸剂，相对于式(II)化合物，三乙胺或苯胺的用量以摩尔计为2.1-2.5倍摩尔量。当式(II)化合物与仅仅式(III)化合物进行酯化反应时(即Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’每组各自相同时)，式(III)化合物与式(II)化合物的摩尔比为2.0-3.0，优选为2.1-2.5；当式(II)化合物与式(III)化合物和式(III’)化合物先后进行酯化反应时(即Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’这几组中至少一组不同时)，式(III)化合物和式(III’)化合物各自与式(II)化合物的摩尔比为1.0-2.0，优选为1.1-1.5。 After completion of the reaction of the crotonic acid with the acid halogenating reagent, the compound of formula (II) is obtained. The compound can be completely separated and then reacted with the compound of formula (III) or reacted with the compound of formula (III) and the compound of formula (III ') successively, or the excess acid halogenation reagent can be removed by rotary evaporation followed by vacuum distillation , And then introduce the compound of formula (III) to continue the reaction or continue the reaction with the compound of formula (III) and the compound of formula (III ') successively. Since the reaction of the compound of formula (II) with the compound of formula (III) and the sequential reaction of the compound of formula (II) with the compound of formula (III) and the compound of formula (III ') will produce acidic hydrogen halide, in order to prevent the acidic substance from causing Side reactions reduce the final yield. The reaction in step 1) is usually carried out in the presence of an acid trapping agent. As the acid trapping agent, triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, or any mixture thereof can be used. The amount or total amount of acid trapping agent (in the case where the compound of formula (II) and the compound of formula (III) and the compound of formula (III ') are reacted successively) should generally be such that the molar ratio of the acid trapping agent to the compound of formula (II) is 2.0- 3.0, preferably 2.1-2.5. For example, when triethylamine or aniline is used as the acid trapping agent, the amount of triethylamine or aniline used is 2.1 to 2.5 times the molar amount relative to the compound of formula (II). When the compound of formula (II) and only the compound of formula (III) undergo an esterification reaction (i.e. Z and Z ', W and W', R ₀ and R ₀ ', R ₁ and R ₁ ', R ₂ and R ₂ ' , M and m 'and n1 and n1' are the same for each group), the molar ratio of the compound of formula (III) to the compound of formula (II) is 2.0-3.0, preferably 2.1-2.5; when the compound of formula (II) and formula (III) When the compound and the compound of formula (III ') are successively subjected to an esterification reaction (that is, Z and Z', W and W ', R ₀ and R ₀ ', R ₁ and R ₁ ', R ₂ and R ₂ ', m and m 'and at least one of n1 and n1' are different), the molar ratio of the compound of formula (III) and the compound of formula (III ') to the compound of formula (II) is 1.0-2.0, preferably 1.1 -1.5.

式(III)化合物和式(III’)化合物以及俘酸剂各自独立地可以以本身引入，也可以在溶剂中的溶液引入。如果它们各自以溶液引入，优选它们使用的溶剂相同。对此，可以使用的溶剂包括二氯甲烷、四氢呋喃、正己烷、石油醚、1,4-二氧六环和乙腈。溶剂的用量通常为式(III)化合物用量的2-10倍重量(当Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’每组各自相同时)，或者溶剂的用量为式(III)化合物与式(III’)化合物总量的2-10倍重量(当Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’这几组中至少一组不同时)。式(II)化合物与式(III)化合物或式(III’)化合物的反应通常在20-30℃的温度下进行，优选在室温下进行。反应时间各自通常为10-20小时。 The compound of the formula (III) and the compound of the formula (III ′) and the acid trapping agent may be independently introduced by themselves, or may be introduced as a solution in a solvent. If they are each introduced as a solution, it is preferred that they use the same solvent. For this, solvents that can be used include dichloromethane, tetrahydrofuran, n-hexane, petroleum ether, 1,4-dioxane, and acetonitrile. The amount of solvent is usually 2-10 times the weight of the compound of formula (III) (when Z and Z ', W and W', R ₀ and R ₀ ', R ₁ and R ₁ ', R ₂ and R ₂ ', m and m 'and n1 and n1' are the same for each group), or the amount of solvent is 2-10 times the total weight of the compound of formula (III) and the compound of formula (III ') (when Z and Z', W and (At least one of W ', R ₀ and R ₀ ', R ₁ and R ₁ ', R ₂ and R ₂ ', m and m ', and n1 and n1' are different groups). The reaction of the compound of formula (II) with the compound of formula (III) or the compound of formula (III ') is usually carried out at a temperature of 20-30 ° C, preferably at room temperature. The reaction time is usually 10-20 hours each.

当步骤1)的反应完成之后，将所得产物提纯，即得到式(IV)化合物。为了提纯步骤1)得到的产物，通常先将反应得到的混合物过滤，除去不溶物，滤液用去离子水水洗至水相pH为中性为止，再用无水硫酸镁粉末干燥有机相比如10-12h，最后旋蒸除去多余溶剂后减压蒸馏，得到式(IV)化合物。After the reaction of step 1) is completed, the resulting product is purified to obtain the compound of formula (IV). In order to purify the product obtained in step 1), the mixture obtained by the reaction is usually filtered to remove insoluble materials. The filtrate is washed with deionized water until the pH of the aqueous phase is neutral, and then dried with anhydrous magnesium sulfate powder. After 12h, the excess solvent was finally removed by rotary evaporation and then distilled under reduced pressure to obtain the compound of formula (IV).

通过步骤1)，得到式(IV)化合物。该化合物含有烯属双键，该烯属双键能够与含有巯基的化合物(即硫醇)发生点击化学反应，即可快速、高效率地获得本发明式(I)化合物。Through step 1), the compound of formula (IV) is obtained. The compound contains an olefinic double bond, and the olefinic double bond can cause a click chemical reaction with a thiol-containing compound (ie, thiol), and the compound of formula (I) of the present invention can be obtained quickly and efficiently.

因此，在本发明方法的步骤2)中，使式(IV)化合物与式(V)化合物反应，Therefore, in step 2) of the method of the present invention, the compound of formula (IV) is reacted with the compound of formula (V),

其中R ₅、R ₆和n3如对式(I)化合物所定义， Where R ₅ , R ₆ and n3 are as defined for the compound of formula (I),

得到式(I)化合物。The compound of formula (I) is obtained.

步骤2)中的反应通过硫醇与烯烃的点击化学反应进行。为了实现步骤2)中的反应，通常有如下两种方式，即步骤2a)和步骤2b)。The reaction in step 2) is carried out by the click chemical reaction of thiol and olefin. In order to achieve the reaction in step 2), there are generally two ways as follows, step 2a) and step 2b).

在步骤2a)中，在自由基引发剂存在下和在无氧气的条件下，使式(IV)化合物与式(V)化合物反应。这里采用的自由基引发剂类型没有特别的要求，只要在反应温度下可以分解产生自由基即可。作为这里自由基引发剂的实例，可以提及偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过氧化二苯甲酰或其任意混合物。In step 2a), the compound of formula (IV) is reacted with the compound of formula (V) in the presence of a free radical initiator and in the absence of oxygen. The type of free radical initiator used here is not particularly required, as long as it can decompose to generate free radicals at the reaction temperature. As examples of free radical initiators here, mention may be made of azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide or any mixture thereof.

在步骤2b)中，使式(IV)化合物和式(V)化合物在紫外光照射下反应。为了产生反应需要的紫外光，可以使用紫外灯，例如发射波段为300-600nm的紫外灯。In step 2b), the compound of formula (IV) and the compound of formula (V) are reacted under irradiation of ultraviolet light. In order to generate the ultraviolet light required for the reaction, an ultraviolet lamp can be used, for example, an ultraviolet lamp with an emission band of 300-600 nm.

在步骤2a)中，式(IV)化合物与式(V)化合物的用量应使得，式(IV)化合物与式(V)化合物的摩尔比通常为0.8-1.5，优选为0.9-1.1。步骤2)中的反应温度通常为40-110℃，优选50-100℃。该反应的时间通常为6-15小时，优选7-11小时。In step 2a), the amount of the compound of formula (IV) and the compound of formula (V) should be such that the molar ratio of the compound of formula (IV) to the compound of formula (V) is usually 0.8-1.5, preferably 0.9-1.1. The reaction temperature in step 2) is usually 40-110 ° C, preferably 50-100 ° C. The reaction time is usually 6-15 hours, preferably 7-11 hours.

步骤2a)中的反应通常在有机溶剂存在下进行。对于步骤2a)而言，由于反应是在高温下进行的，因此所使用的溶剂必须具有高沸点。作为有机溶剂的实例，可以使用二甲基甲酰胺(DMF)和甲苯。可使用单一种溶剂，也可使用两种或更多种溶剂的混合物。对于溶剂的用量，没有特别的限制，只要能将各反应物充分溶解即可。通常而言，溶剂的用量为反应物总量的2-10倍重量。The reaction in step 2a) is usually carried out in the presence of an organic solvent. For step 2a), since the reaction is carried out at a high temperature, the solvent used must have a high boiling point. As examples of organic solvents, dimethylformamide (DMF) and toluene can be used. A single solvent may be used, or a mixture of two or more solvents may be used. There is no particular restriction on the amount of solvent used, as long as each reactant can be fully dissolved. Generally speaking, the amount of solvent is 2-10 times the total weight of the reactants.

在步骤2a)反应完成之后，将所得产物提纯，即得到式(I)化合物。为了提纯步骤2a)得到的产物，通常将反应得到的粗产物经过旋蒸和减压蒸馏来纯化，得到式(I)化合物。步骤2)得到的产物的产率通常在95％以上。After the reaction of step 2a) is completed, the resulting product is purified to obtain the compound of formula (I). In order to purify the product obtained in step 2a), the crude product obtained by the reaction is usually purified by rotary evaporation and distillation under reduced pressure to obtain the compound of formula (I). The yield of the product obtained in step 2) is usually above 95%.

在步骤2b)中，式(IV)化合物与式(V)化合物的用量应使得，式(IV)化合物与式(V)化合物的摩尔比通常为0.8-1.5，优选为0.9-1.0。步骤2b)中的反应温度通常为室温。该反应的时间通常为20-40min，优选25-35min。步骤2b)中的反应转化率非常高，产率通常在99％以上。因此，当式(IV)化合物与式(V)化合物的用量为等摩尔量时，无需提纯。因而相比于步骤2a)的反应，步骤2b)中的反应操作简便，耗时少，产率更高。In step 2b), the amount of the compound of formula (IV) and the compound of formula (V) should be such that the molar ratio of the compound of formula (IV) to the compound of formula (V) is usually 0.8-1.5, preferably 0.9-1.0. The reaction temperature in step 2b) is usually room temperature. The reaction time is usually 20-40 min, preferably 25-35 min. The conversion rate of the reaction in step 2b) is very high, and the yield is usually above 99%. Therefore, when the amount of the compound of formula (IV) and the compound of formula (V) is equimolar, no purification is required. Therefore, compared to the reaction in step 2a), the reaction in step 2b) is simple, time-consuming, and has a higher yield.

根据本发明的第三个方面，提供了一种聚合物，该聚合物通过将本发明的式(I)化合物开环聚合而得到。该开环聚合优选通过阳离子光固化开环聚合实现。该阳离子光固化开环聚合尤其在光引发剂存在下进行紫外光固化来实现。According to a third aspect of the present invention, there is provided a polymer obtained by ring-opening polymerization of the compound of formula (I) of the present invention. The ring-opening polymerization is preferably achieved by cationic photo-curing ring-opening polymerization. The cationic photo-curing ring-opening polymerization is achieved by ultraviolet curing in the presence of a photoinitiator.

作为开环聚合的光引发剂，常用的主要有碘鎓盐和硫鎓盐，如下式化合物A(二苯基-(4-苯基硫)苯基锍六氟锑酸盐，CAS NO：8945-2-37-9))、化合物B((硫化-二-4,1-仲苯基)-双(二苯基锍)-双-六氟锑酸盐，CAS NO：71449-78-0)或其混合物。例如，常州强力电子新材料有限公司的商品TR-PAG-201，其为化合物A和化合物B的总量为50％的丙烯酸酯溶液，此处的丙烯酸酯为4-甲基-1,3-二氧戊-2-酮(CAS NO：108-32-7)。As photoinitiators for ring-opening polymerization, iodonium salts and sulfonium salts are commonly used. Compound A (diphenyl- (4-phenylsulfide) phenylsulfonium hexafluoroantimonate, CAS NO: 8945 -2-37-9)), compound B ((sulfide-di-4,1-sec-phenyl) -bis (diphenylsulfonium) -bis-hexafluoroantimonate, CAS NO: 71449-78-0 ) Or mixtures thereof. For example, the commercial product TR-PAG-201 of Changzhou Qiangli Electronic New Material Co., Ltd. is a 50% acrylate solution of compound A and compound B, where the acrylate is 4-methyl-1,3- Dioxol-2-one (CAS NO: 108-32-7).

本发明的含氟可阳离子光固化单体化合物中即包含可光聚合结构部分，又包括基本上全氟化的烷基结构，并且这二者之间还连接有丁二酸酯结构部分，这使得该单体聚合后形成的聚合物涂层具有高的表面硬度、极低的表面能，表现出疏水疏油的优良性能，尤其是抗油性沾污非常好。The fluorine-containing cationic photocurable monomer compound of the present invention contains both a photopolymerizable structural part and a substantially perfluorinated alkyl structure, and a succinate structural part is connected between the two, which The polymer coating formed after the polymerization of the monomer has high surface hardness and extremely low surface energy, and exhibits excellent performance of hydrophobicity and oleophobicity, especially excellent resistance to oil stains.

因此，根据本发明的第四个方面，提供了一种可光固化组合物，该组合物包含本发明的式(I)化合物作为聚合单体。该可光固化组合物除了包含本发明的式(I)化合物以外，还可包含光引发剂以及其它含有乙烯基醚双键、脂环族环氧基、环氧乙烷基或者氧杂环丁烷基等可阳离子光固化基团的单体、低聚物，例如，湖北固润科技有限公司的商品GR-OXT-1(CAS NO:3047-32-3),GR-OXT-7(CAS NO:483303-25-9)。本发明可光固化组合物可以为光固化涂料组合物、光固化油墨组合物、光致抗蚀组合物等。该组合物在固化后其表面硬度高，具有极低的表面能，疏水疏油性能良好，尤其是抗油性沾污非常好。Therefore, according to the fourth aspect of the present invention, there is provided a photocurable composition comprising the compound of formula (I) of the present invention as a polymerizable monomer. In addition to the compound of formula (I) of the present invention, the photocurable composition may also contain a photoinitiator and other containing vinyl ether double bond, alicyclic epoxy group, oxirane group or oxetane Monomers and oligomers of cationic photocurable groups such as alkyl groups, such as GR-OXT-1 (CAS NO: 3047-32-3), GR-OXT-7 (CAS NO: 483303-25-9). The photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After curing, the composition has high surface hardness, extremely low surface energy, good hydrophobic and oleophobic properties, especially good resistance to oil stains.

根据本发明的最后一个方面，提供一种光固化材料，该材料通过将本发明的可光固化组合物光固化而获得。该光固化材料由于包含本发明式(I)化合物作为可光固化单体的缘故具有高的表面硬度，极低的表面能，优良的疏水疏油性，尤其是抗油性沾污非常好。According to the last aspect of the present invention, there is provided a photocurable material obtained by photocuring the photocurable composition of the present invention. The photocurable material has high surface hardness, extremely low surface energy, excellent hydrophobicity and oleophobicity, especially good resistance to oily stains because it contains the compound of formula (I) of the present invention as a photocurable monomer.

实施例Examples

以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。The present invention will be further described below with reference to specific embodiments, but it should not be construed as limiting the protection scope of the present invention.

实施例1：化合物C-1的合成Example 1: Synthesis of compound C-1

将11.61g(0.1mol)的富马酸和35.69g(0.3mol)的二氯亚砜混合均匀后在70℃的条件下搅拌5h。之后先旋蒸后减压蒸馏除去多余的二氯亚砜后，向剩余液体中加入200mL的二氯甲烷和18.48g(0.22mol)碳酸氢钠。在氮气氛围中将前述混合液通过冰浴降温到零摄氏度左右，然后向其中逐滴加入25.52g(0.22mol)3-乙基-3-羟甲基氧杂环丁烷。滴加完毕后在室温中继续反应10h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸二(3-乙基-3-羟甲基氧杂环丁烷)酯25.27g，产率81％。11.61 g (0.1 mol) of fumaric acid and 35.69 g (0.3 mol) of dichlorosulfoxide were mixed uniformly and stirred at 70 ° C. for 5 h. After spin-distilling and distilling off excess dichlorosulfoxide under reduced pressure, 200 mL of methylene chloride and 18.48 g (0.22 mol) of sodium bicarbonate were added to the remaining liquid. The aforementioned mixed solution was cooled to about zero degrees Celsius through an ice bath in a nitrogen atmosphere, and then 25.52 g (0.22 mol) of 3-ethyl-3-hydroxymethyloxetane was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 10 hours. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure. Di (3-ethyl-3-hydroxymethyloxetane) maleate 25.27g, 81% yield.

在氮气氛围下，将3.12g(0.01mol)的富马酸二(3-乙基-3-羟甲基氧杂环丁烷)酯、3.08g(0.011mol)的1H,1H,2H,2H-全氟己硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至65℃，搅拌8h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-1，共5.68g，产率96％。Under a nitrogen atmosphere, combine 3.12 g (0.01 mol) of bis (3-ethyl-3-hydroxymethyloxetane) fumarate and 3.08 g (0.011 mol) of 1H, 1H, 2H, 2H -Perfluorohexyl mercaptan, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then warmed to 65 ° C and stirred for 8h. After the reaction was completed, after the reaction system was cooled to room temperature, the excess toluene was removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-1, a total of 5.68 g, and a yield of 96%.

将3.12g(0.01mol)的富马酸二(3-乙基-3-羟甲基氧杂环丁烷)酯与3.08g(0.011mol)的1H,1H,2H,2H-全氟己硫醇加入到单口烧杯中混合均匀。然后将其置于紫外灯(产生的辐射波段为300-600nm)下曝光30min，得到最终产物C-1，共5.86g，产率99％。3.12g (0.01mol) fumaric acid bis (3-ethyl-3-hydroxymethyloxetane) ester and 3.08g (0.011mol) 1H, 1H, 2H, 2H-perfluorohexylsulfide Add alcohol to a single-mouth beaker and mix well. Then it was placed under an ultraviolet lamp (the generated radiation band is 300-600nm) and exposed for 30min to obtain the final product C-1, a total of 5.86g, with a yield of 99%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δδ4.40(t,J＝6.4Hz,4H),4.18(d,J＝6.0Hz,2H),4.12(d,J＝5.9Hz,2H),3.94(s,4H),3.78(t,J＝7.0Hz,1H),3.36–3.18(m,2H),3.11(td,J＝12.5,3.4Hz,1H),2.97(dd,J＝12.4,7.0Hz,1H),2.66–2.49(m,1H),1.69(q,J＝8.0Hz,4H),0.89(t,J＝8.0Hz,3H),0.80(t,J＝8.0Hz,3H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ δ 4.40 (t, J = 6.4 Hz, 4H), 4.18 (d, J = 6.0 Hz, 2H), 4.12 (d, J = 5.9 Hz , 2H), 3.94 (s, 4H), 3.78 (t, J = 7.0Hz, 1H), 3.36-3.18 (m, 2H), 3.11 (td, J = 12.5, 3.4Hz, 1H), 2.97 (dd, J = 12.4, 7.0Hz, 1H), 2.66-2.49 (m, 1H), 1.69 (q, J = 8.0Hz, 4H), 0.89 (t, J = 8.0Hz, 3H), 0.80 (t, J = 8.0 Hz, 3H).

实施例2：化合物C-2的合成Example 2: Synthesis of compound C-2

重复实施例1的方法，不同之处在于：将1H,1H,2H,2H-全氟己硫醇更换成1H,1H,2H,2H-全氟辛硫醇。得到最终产物C-2，共6.64g，产率96％。The method of Example 1 was repeated, except that: 1H, 1H, 2H, 2H-perfluorohexyl mercaptan was replaced with 1H, 1H, 2H, 2H-perfluorooctane mercaptan. The final product C-2 was obtained with a total of 6.64 g and a yield of 96%.

实施例3：化合物C-3的合成Example 3: Synthesis of compound C-3

重复实施例1的方法，不同之处在于：将1H,1H,2H,2H-全氟己硫醇更换成1H,1H,2H,2H-全氟癸硫醇。得到最终产物C-3，共7.6g，产率96％。The method of Example 1 was repeated, except that: 1H, 1H, 2H, 2H-perfluorohexanethiol was replaced with 1H, 1H, 2H, 2H-perfluorodecanethiol. The final product C-3 was obtained with a total of 7.6 g and a yield of 96%.

实施例4：化合物C-4的合成Example 4: Synthesis of compound C-4

将11.61g(0.1mol)的富马酸和38.08g(0.3mol)的草酰氯混合均匀后在75℃的条件下搅拌6h。之后先旋蒸后减压蒸馏除去多余的草酰氯，向剩余液体中加入200mL的二氯甲烷。在氮气氛围中将前述混合液通过冰浴降温到零摄氏度左右，然后向其中逐滴加入15.54g(0.21mol)的缩水甘油和23.23g(0.23mol)三乙胺的混合液。滴加完毕后在室温继续反应15h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸二缩水甘油酯18.47g，产率81％。11.61 g (0.1 mol) of fumaric acid and 38.08 g (0.3 mol) of oxalyl chloride were mixed uniformly and stirred at 75 ° C. for 6 h. Afterwards, the oxalyl chloride was removed by rotary evaporation and then reduced pressure, and 200 mL of methylene chloride was added to the remaining liquid. In the nitrogen atmosphere, the aforementioned mixed liquid was cooled to about zero degrees Celsius through an ice bath, and then a mixed liquid of 15.54 g (0.21 mol) of glycidol and 23.23 g (0.23 mol) of triethylamine was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 15h. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure. 18.47 g of diglycidyl maleate with a yield of 81%.

在氮气氛围下，将2.28g(0.01mol)的富马酸二缩水甘油酯、3.36g(0.012mol)的1H,1H,2H,2H-全氟己硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至75℃，搅拌7h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-4，共4.88g，产率96％。Under a nitrogen atmosphere, couple 2.28 g (0.01 mol) of diglycidyl fumarate, 3.36 g (0.012 mol) of 1H, 1H, 2H, 2H-perfluorohexyl mercaptan, 0.0328 g (0.0002 mol) Azodiisobutyronitrile and 10 mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then warmed to 75 ° C and stirred for 7h. After the reaction is completed, after the reaction system is cooled to room temperature, the excess toluene is removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-4, a total of 4.88 g, and a yield of 96%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.69(dd,J＝12.4,7.0Hz,1H),4.53(dd,J＝12.4,7.0Hz,1H),4.31(dd,J＝12.3,7.0Hz,1H),4.21(dd,J＝12.4,6.9Hz,1H),3.97(t,J＝7.0Hz,1H),3.26(dd,J＝12.5,7.0Hz,1H),3.23–3.14(m,1H),3.09(dp,J＝23.6,7.0Hz,2H),2.95–2.74(m,3H),2.67(dd,J＝7.1,5.0Hz,1H),2.61(dd,J＝7.0,5.0Hz,1H),2.42(dd,J＝7.0,5.0Hz,1H),2.37(dd,J＝7.0,5.1Hz,1H),2.36–2.20(m,1H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.69 (dd, J = 12.4, 7.0 Hz, 1H), 4.53 (dd, J = 12.4, 7.0 Hz, 1H), 4.31 (dd, J = 12.3, 7.0 Hz, 1H), 4.21 (dd, J = 12.4, 6.9 Hz, 1H), 3.97 (t, J = 7.0 Hz, 1H), 3.26 (dd, J = 12.5, 7.0 Hz, 1H), 3.23–3.14 (m, 1H), 3.09 (dp, J = 23.6, 7.0Hz, 2H), 2.95–2.74 (m, 3H), 2.67 (dd, J = 7.1, 5.0Hz, 1H), 2.61 (dd, J = 7.0, 5.0 Hz, 1H), 2.42 (dd, J = 7.0, 5.0 Hz, 1H), 2.37 (dd, J = 7.0, 5.1 Hz, 1H), 2.36-2.20 (m, 1H).

实施例5：化合物C-5的合成Example 5: Synthesis of Compound C-5

重复实施例4的方法，不同之处在于：将1H,1H,2H,2H-全氟己硫醇更换成1H,1H,2H,2H-全氟辛硫醇。得到最终产物C-5，共5.84g，产率96％。The method of Example 4 was repeated, except that: 1H, 1H, 2H, 2H-perfluorohexyl mercaptan was replaced with 1H, 1H, 2H, 2H-perfluorooctane mercaptan. The final product C-5 was obtained with a total of 5.84 g and a yield of 96%.

实施例6：化合物C-6的合成Example 6: Synthesis of compound C-6

重复实施例4的方法，不同之处在于：将1H,1H,2H,2H-全氟己硫醇更换成1H,1H,2H,2H-全氟癸硫醇。得到最终产物C-6，共6.80g，产率96％。The method of Example 4 was repeated, except that: 1H, 1H, 2H, 2H-perfluorohexanethiol was replaced with 1H, 1H, 2H, 2H-perfluorodecanethiol. The final product C-6 was obtained with a total of 6.80 g and a yield of 96%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.69(dd,J＝12.4,7.0Hz,1H),4.53(dd,J＝12.4,7.0Hz,1H),4.31(dd,J＝12.3,7.0Hz,1H),4.21(dd,J＝12.4,6.9Hz,1H),3.97(t,J＝7.0Hz,1H),3.26(dd,J＝12.5,7.0Hz,1H),3.23–3.14(m,1H),3.09(dp,J＝23.6,7.0Hz,2H),2.95–2.74(m,3H),2.67(dd,J＝7.1,5.0Hz,1H),2.61(dd,J＝7.0,5.0Hz,1H),2.42(dd,J＝7.0,5.0Hz,1H),2.37(dd,J＝7.0, 5.1Hz,1H),2.36–2.20(m,1H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.69 (dd, J = 12.4, 7.0 Hz, 1H), 4.53 (dd, J = 12.4, 7.0 Hz, 1H), 4.31 (dd, J = 12.3, 7.0 Hz, 1H), 4.21 (dd, J = 12.4, 6.9 Hz, 1H), 3.97 (t, J = 7.0 Hz, 1H), 3.26 (dd, J = 12.5, 7.0 Hz, 1H), 3.23–3.14 (m, 1H), 3.09 (dp, J = 23.6, 7.0Hz, 2H), 2.95–2.74 (m, 3H), 2.67 (dd, J = 7.1, 5.0Hz, 1H), 2.61 (dd, J = 7.0, 5.0 Hz, 1H), 2.42 (dd, J = 7.0, 5.0 Hz, 1H), 2.37 (dd, J = 7.0, 5.1 Hz, 1H), 2.36-2.20 (m, 1H).

实施例7：化合物C-7的合成Example 7: Synthesis of compound C-7

将11.61g(0.1mol)的富马酸和50.80g(0.4mol)的草酰氯混合均匀后在80℃的条件下搅拌5h。之后先旋蒸后减压蒸馏除去多余的草酰氯，向剩余液体中加入200mL的二氯甲烷。在氮气氛围中将前述混合液通过冰浴降温到零摄氏度左右，然后向其中逐滴加入17.02g(0.23mol)的缩水甘油和23.23g(0.23mol)三乙胺的混合液。滴加完毕后在室温继续反应16h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸二缩水甘油酯18.47g，产率81％。11.61 g (0.1 mol) of fumaric acid and 50.80 g (0.4 mol) of oxalyl chloride were mixed uniformly and stirred at 80 ° C. for 5 h. Afterwards, the oxalyl chloride was removed by rotary evaporation and then reduced pressure, and 200 mL of methylene chloride was added to the remaining liquid. The aforementioned mixed solution was cooled to about zero degrees Celsius through an ice bath in a nitrogen atmosphere, and then a mixed solution of 17.02 g (0.23 mol) of glycidol and 23.23 g (0.23 mol) of triethylamine was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 16h. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure. 18.47 g of diglycidyl maleate with a yield of 81%.

在氮气氛围下，将2.28g(0.01mol)的富马酸二缩水甘油酯、4.12g(0.014mol)的1H,1H,1H,2H,2H,3H-全氟庚烷-3-硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至80℃，搅拌9h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-7，共5.15g，产率96％。Under a nitrogen atmosphere, combine 2.28g (0.01mol) of diglycidyl fumarate, 4.12g (0.014mol) of 1H, 1H, 1H, 2H, 2H, 3H-perfluoroheptane-3-thiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then warmed to 80 ° C and stirred for 9h. After the reaction is completed, after the reaction system is cooled to room temperature, the excess toluene is removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-7, a total of 5.15 g, and a yield of 96%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.59(ddd,J＝12.5,7.0,3.1Hz,2H),4.46(dd,J＝12.4,7.1Hz,1H),4.23(dd,J＝12.5,7.0Hz,1H),4.17(t,J＝6.9Hz,1H),3.21(dd,J＝12.4,7.1Hz,1H),3.14(p,J＝7.0Hz,1H),3.06(p,J＝7.0Hz,1H),3.03–2.85(m,2H),2.69(td,J＝6.9,5.0Hz,2H),2.55(dd,J＝7.0,5.0Hz,1H),2.39(dd,J＝7.1,5.0Hz,1H),2.06(tq,J＝12.4,8.0Hz,1H),1.54(dqd,J＝12.2,8.0,2.8Hz,1H),0.88(t,J＝8.0Hz,3H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.59 (ddd, J = 12.5, 7.0, 3.1 Hz, 2H), 4.46 (dd, J = 12.4, 7.1 Hz, 1H), 4.23 ( dd, J = 12.5, 7.0 Hz, 1H), 4.17 (t, J = 6.9 Hz, 1H), 3.21 (dd, J = 12.4, 7.1 Hz, 1H), 3.14 (p, J = 7.0 Hz, 1H), 3.06 (p, J = 7.0 Hz, 1H), 3.03--2.85 (m, 2H), 2.69 (td, J = 6.9, 5.0 Hz, 2H), 2.55 (dd, J = 7.0, 5.0 Hz, 1H), 2.39 (dd, J = 7.1, 5.0 Hz, 1H), 2.06 (tq, J = 12.4, 8.0 Hz, 1H), 1.54 (dqd, J = 12.2, 8.0, 2.8 Hz, 1H), 0.88 (t, J = 8.0 Hz, 3H).

实施例8：化合物C-8的合成Example 8: Synthesis of compound C-8

将11.61g(0.1mol)的富马酸和50.80g(0.4mol)的草酰氯混合均匀后在70℃的条件下搅拌4h。之后先旋蒸后减压蒸馏除去多余的草酰氯，向剩余液体中加入200mL的二氯甲烷。在氮气氛围中将前述混合液通过冰浴降温到零摄氏度左右，然后向其中逐滴加入21.12g(0.24mol)3,4-环氧-1-丁醇和20.46g(0.22mol)苯胺的混合液。滴加完毕后在室温继续反应18h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸二(1,2-环氧-4-羟基丁烷)酯20.74g，产率81％。11.61 g (0.1 mol) of fumaric acid and 50.80 g (0.4 mol) of oxalyl chloride were mixed uniformly and stirred at 70 ° C. for 4 h. Afterwards, the oxalyl chloride was removed by rotary evaporation and then reduced pressure, and 200 mL of methylene chloride was added to the remaining liquid. In a nitrogen atmosphere, the aforementioned mixed solution was cooled to about zero degrees Celsius through an ice bath, and then a mixed solution of 21.12g (0.24mol) 3,4-epoxy-1-butanol and 20.46g (0.22mol) aniline was added dropwise thereto . After the dropwise addition, the reaction was continued at room temperature for 18h. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure. Di (1,2-epoxy-4-hydroxybutane) maleate 20.74g, yield 81%.

在氮气氛围下，将2.56g(0.01mol)的富马酸二(1,2-环氧-4-羟基丁烷)酯、4.20g(0.015mol)的1H,1H,2H,2H-全氟己硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至90℃，搅拌10h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-8，共5.15g，产率96％。Under a nitrogen atmosphere, 2.56 g (0.01 mol) of fumaric acid bis (1,2-epoxy-4-hydroxybutane) ester, 4.20 g (0.015 mol) of 1H, 1H, 2H, 2H-perfluoro Hexanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then warmed to 90 ° C and stirred for 10h. After the reaction is completed, after the reaction system is cooled to room temperature, the excess toluene is removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-8, a total of 5.15 g, and a yield of 96%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.59(dt,J＝12.4,2.9Hz,1H),4.01–3.82(m,3H),3.80(t,J＝6.9Hz,1H),3.31(td,J＝12.5,3.2Hz,1H),3.16(dd,J＝12.4,7.1Hz,1H),3.10(td,J＝12.5,3.1Hz,1H),3.02(dd,J＝12.4,7.0Hz,1H),2.70(p,J＝7.0Hz,1H),2.68–2.59(m,2H),2.58(dd,J＝6.9,5.0Hz,1H),2.54–2.32(m,3H),2.34–2.19(m,1H),1.84–1.73(m,1H),1.73–1.61(m,3H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.59 (dt, J = 12.4, 2.9 Hz, 1H), 4.01–3.82 (m, 3H), 3.80 (t, J = 6.9 Hz, 1H), 3.31 (td, J = 12.5, 3.2 Hz, 1H), 3.16 (dd, J = 12.4, 7.1 Hz, 1H), 3.10 (td, J = 12.5, 3.1 Hz, 1H), 3.02 (dd, J = 12.4, 7.0 Hz, 1H), 2.70 (p, J = 7.0 Hz, 1H), 2.68–2.59 (m, 2H), 2.58 (dd, J = 6.9, 5.0 Hz, 1H), 2.54–2.32 (m, 3H), 2.34–2.19 (m, 1H), 1.84–1.73 (m, 1H), 1.73–1.61 (m, 3H).

实施例9：化合物C-9的合成Example 9: Synthesis of compound C-9

将11.61g(0.1mol)的富马酸和50.80g(0.4mol)的草酰氯混合均匀后在80℃的条件下搅拌6h。之后先旋蒸后减压蒸馏除去多余的草酰氯，向剩余液体中加入200mL的二氯甲烷和23.31g(0.22mol)碳酸钠。在氮气氛围中将前述混合液通过冰浴降温到零摄氏度左右，然后向其中逐滴加入25.50g(0.25mol)1,2-环氧-3-羟基戊烷。滴加完毕后在室温继续反应20h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸二(1,2-环氧-3-羟基戊烷)酯23.00g，产率81％。11.61 g (0.1 mol) of fumaric acid and 50.80 g (0.4 mol) of oxalyl chloride were mixed uniformly and stirred at 80 ° C. for 6 h. Afterwards, the oxalyl chloride was removed by rotary evaporation and then reduced pressure, and 200 mL of methylene chloride and 23.31 g (0.22 mol) of sodium carbonate were added to the remaining liquid. In a nitrogen atmosphere, the aforementioned mixed solution was cooled to about zero degrees Celsius through an ice bath, and then 25.50 g (0.25 mol) of 1,2-epoxy-3-hydroxypentane was added dropwise thereto. After the dropwise addition, the reaction was continued at room temperature for 20 hours. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure. 23.00 g of bis (1,2-epoxy-3-hydroxypentane) maleate with a yield of 81%.

在氮气氛围下，将2.84g(0.01mol)的富马酸(1,2-环氧-3-羟基戊烷)酯、3.08g(0.011mol)的1H,1H,2H,2H-全氟己硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至100℃，搅拌7h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-9，共5.41g，产率96％。Under a nitrogen atmosphere, 2.84 g (0.01 mol) of fumaric acid (1,2-epoxy-3-hydroxypentane) ester and 3.08 g (0.011 mol) of 1H, 1H, 2H, 2H-perfluorohexane Mercaptan, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then heated to 100 ° C and stirred for 7h. After the reaction is completed, after the reaction system is cooled to room temperature, the excess toluene is removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-9, a total of 5.41 g, and a yield of 96%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.60(dq,J＝18.5,7.1Hz,2H),3.97(t,J＝7.0Hz,1H),3.47(td,J＝12.5,3.3Hz,1H),3.24(dd,J＝12.4,7.0Hz,1H),3.08(q,J＝7.0Hz,1H),3.08–2.97(m,2H),2.84(dd,J＝12.4,7.0Hz,1H),2.53–2.32(m,4H),2.27(dd,J＝7.1,5.0Hz,1H),1.99(ttd,J＝20.9,12.5,2.7Hz,1H),1.74–1.63(m,1H),1.65–1.54(m,1H),1.34–1.16(m,2H),0.86(q,J＝7.9Hz,6H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.60 (dq, J = 18.5, 7.1 Hz, 2H), 3.97 (t, J = 7.0 Hz, 1H), 3.47 (td, J = 12.5, 3.3Hz, 1H), 3.24 (dd, J = 12.4, 7.0Hz, 1H), 3.08 (q, J = 7.0Hz, 1H), 3.08-2.97 (m, 2H), 2.84 (dd, J = 12.4 , 7.0Hz, 1H), 2.53–2.32 (m, 4H), 2.27 (dd, J = 7.1, 5.0Hz, 1H), 1.99 (ttd, J = 20.9, 12.5, 2.7Hz, 1H), 1.74–1.63 ( m, 1H), 1.65–1.54 (m, 1H), 1.34–1.16 (m, 2H), 0.86 (q, J = 7.9Hz, 6H).

实施例10：化合物C-10的合成Example 10: Synthesis of compound C-10

将11.61g(0.1mol)的富马酸和35.69(0.3mol)的二氯亚砜混合均匀后在75℃的条件下搅拌5h。之后先旋蒸后减压蒸馏除去多余的二氯亚砜后，向剩余液体中加入200mL的二氯甲烷。在氮气氛围中将前述混合液通过冰浴降温到零摄氏度左右，然后向其中逐滴加入25.52g(0.22mol)3-乙基-3-羟甲基氧杂环丁烷和22.22g(0.22mol)三乙胺的混合液。滴加完毕后在室温继续反应12h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸二(3-乙基-3-羟甲基氧杂环丁烷)酯25.27g，产率81％。11.61 g (0.1 mol) of fumaric acid and 35.69 (0.3 mol) of dichlorosulfoxide were mixed uniformly and stirred at 75 ° C. for 5 h. Afterwards, after spin-distilling and distilling off excess dichlorosulfoxide under reduced pressure, 200 mL of methylene chloride was added to the remaining liquid. In a nitrogen atmosphere, the aforementioned mixed solution was cooled to about zero degrees Celsius through an ice bath, and then 25.52g (0.22mol) 3-ethyl-3-hydroxymethyloxetane and 22.22g (0.22mol) were added dropwise thereto ) A mixture of triethylamine. After the dropwise addition, the reaction was continued at room temperature for 12h. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure Di (3-ethyl-3-hydroxymethyloxetane) maleate 25.27g, 81% yield.

在氮气氛围下，将3.12g(0.01mol)的富马酸二(3-乙基-3-羟甲基氧杂环丁烷)酯、1.78g(0.012mol)的2,2,3,3-四氟丙硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至85℃，搅拌8h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-10，共4.41g，产率96％。Under a nitrogen atmosphere, 3.12 g (0.01 mol) of bis (3-ethyl-3-hydroxymethyloxetane) fumarate and 1.78 g (0.012 mol) of 2,2,3,3 -Tetrafluoropropyl mercaptan, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then warmed to 85 ° C and stirred for 8h. After the reaction is completed, after the reaction system is cooled to room temperature, the excess toluene is removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-10, a total of 4.41 g, a yield of 96%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.40(dd,J＝20.3,5.9Hz,4H),4.30–4.15(m,5H),4.02(t,J＝7.0Hz,1H),3.94(s,4H),3.39(td,J＝20.9,12.4Hz,1H),3.27(dd,J＝12.4,7.1Hz,1H),2.84(dd,J＝12.4,7.1Hz,1H),1.69(q,J＝8.0Hz,4H),0.90(t,J＝8.1Hz,3H),0.78(t,J＝8.0Hz,3H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.40 (dd, J = 20.3, 5.9 Hz, 4H), 4.30–4.15 (m, 5H), 4.02 (t, J = 7.0 Hz, 1H), 3.94 (s, 4H), 3.39 (td, J = 20.9, 12.4 Hz, 1H), 3.27 (dd, J = 12.4, 7.1 Hz, 1H), 2.84 (dd, J = 12.4, 7.1 Hz, 1H) ), 1.69 (q, J = 8.0 Hz, 4H), 0.90 (t, J = 8.1 Hz, 3H), 0.78 (t, J = 8.0 Hz, 3H).

实施例11：化合物C-11的合成Example 11: Synthesis of compound C-11

将11.61g(0.1mol)的富马酸和50.8g(0.4mol)的草酰氯混合均匀后在80℃ 的条件搅拌6h。之后先旋蒸后减压蒸馏除去多余的草酰氯后，向剩余液体中加入200mL的二氯甲烷。在氮气氛围中将前述混合液通过冰浴降温到零度左右，然后向其中逐滴加入27.84g(0.24mol)3-乙基-3-羟甲基氧杂环丁烷和25.25g(0.25mol)三乙胺的混合液。滴加完毕后在室温继续反应12h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸二(3-乙基-3-羟甲基氧杂环丁烷)酯25.27g，产率81％。11.61 g (0.1 mol) of fumaric acid and 50.8 g (0.4 mol) of oxalyl chloride were mixed uniformly and stirred at 80 ° C. for 6 h. Then, after evaporating and then distilling off excess oxalyl chloride under reduced pressure, 200 mL of methylene chloride was added to the remaining liquid. In a nitrogen atmosphere, the aforementioned mixed solution was cooled to about zero degree through an ice bath, and then 27.84g (0.24mol) 3-ethyl-3-hydroxymethyloxetane and 25.25g (0.25mol) were added dropwise thereto A mixture of triethylamine. After the dropwise addition, the reaction was continued at room temperature for 12h. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure Di (3-ethyl-3-hydroxymethyloxetane) maleate 25.27g, 81% yield.

在氮气氛围下，将3.12g(0.01mol)的富马酸二(3-乙基-3-羟甲基氧杂环丁烷)酯、4.972g(0.011mol)的1H,1H,2H,2H-3-三氟甲基-全氟-1-丁硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至85℃，搅拌11h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-11，共7.33g，产率96％。Under a nitrogen atmosphere, combine 3.12 g (0.01 mol) of bis (3-ethyl-3-hydroxymethyloxetane) fumarate and 4.972 g (0.011 mol) of 1H, 1H, 2H, 2H -3-Trifluoromethyl-perfluoro-1-butanethiol, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then warmed to 85 ° C and stirred for 11h. After the reaction is completed, after the reaction system is cooled to room temperature, the excess toluene is removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-11, with a total of 7.33 g and a yield of 96%.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.37(d,J＝5.9Hz,1H),4.30(d,J＝6.0Hz,1H),4.22(d,J＝6.0Hz,1H),4.15(d,J＝5.9Hz,1H),3.94(s,2H),3.49–3.34(m,1H),3.27–3.13(m,1H),2.92–2.78(m,1H),1.69(q,J＝8.0Hz,2H),0.86(dt,J＝31.5,8.0Hz,3H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.37 (d, J = 5.9 Hz, 1H), 4.30 (d, J = 6.0 Hz, 1H), 4.22 (d, J = 6.0 Hz , 1H), 4.15 (d, J = 5.9Hz, 1H), 3.94 (s, 2H), 3.49–3.34 (m, 1H), 3.27–3.13 (m, 1H), 2.92–2.78 (m, 1H), 1.69 (q, J = 8.0 Hz, 2H), 0.86 (dt, J = 31.5, 8.0 Hz, 3H).

实施例12：化合物C-12的合成Example 12: Synthesis of compound C-12

将11.61g(0.1mol)的富马酸和50.8g(0.4mol)的草酰氯混合均匀后在80℃的条件下搅拌6h。之后先旋蒸后减压蒸馏除去多余的草酰氯后，向剩余液体中加入200mL的二氯甲烷。在氮气氛围中将前述混合液通过冰浴降温到零摄氏度左右，然后向其中逐滴加入12.76g(0.11mol)3-乙基-3-羟甲基氧杂环丁烷和11.11g(0.11mol)三乙胺的混合液。滴加完毕后在室温继续反应12h。然后再在冰浴下向其中逐滴加入8.14g(0.11mol)的缩水甘油和11.11g(0.11mol)三乙胺的混合液。滴加完毕后在室温继续反应12h。反应完毕后过滤掉不溶物，滤液用水洗，洗至水相pH到中性为止，之后用无水硫酸镁粉末干燥有机相12h，最后旋蒸除去多余二氯甲烷，减压蒸馏得到中间产物富马酸(3-乙基-3-羟甲基氧杂环丁烷)(缩水甘油)酯21.89g，产率81％。11.61 g (0.1 mol) of fumaric acid and 50.8 g (0.4 mol) of oxalyl chloride were mixed uniformly and stirred at 80 ° C. for 6 h. Then, after evaporating and then distilling off excess oxalyl chloride under reduced pressure, 200 mL of methylene chloride was added to the remaining liquid. In a nitrogen atmosphere, the aforementioned mixed solution was cooled to about zero degrees Celsius through an ice bath, and then 12.76g (0.11mol) of 3-ethyl-3-hydroxymethyloxetane and 11.11g (0.11mol) were added dropwise thereto ) A mixture of triethylamine. After the dropwise addition, the reaction was continued at room temperature for 12h. Then, a mixed solution of 8.14 g (0.11 mol) of glycidol and 11.11 g (0.11 mol) of triethylamine was added dropwise thereto under an ice bath. After the dropwise addition, the reaction was continued at room temperature for 12h. After the reaction was completed, the insoluble materials were filtered off, and the filtrate was washed with water until the pH of the aqueous phase was neutral, and then the organic phase was dried with anhydrous magnesium sulfate powder for 12h. Finally, the excess dichloromethane was removed by rotary evaporation, and the intermediate product was distilled under reduced pressure. Maleic acid (3-ethyl-3-hydroxymethyloxetane) (glycidyl) ester 21.89g, yield 81%.

在氮气氛围下，将2.70g(0.01mol)的富马酸(3-乙基-3-羟甲基氧杂环丁烷)(缩水甘油)酯、3.08g(0.011mol)的1H,1H,2H,2H-全氟己硫醇、0.0328g(0.0002mol)的偶氮二异丁腈和10mL的甲苯加入到三口烧瓶中混合均匀。然后将反应混合物升温至85℃，搅拌8h。反应完毕后待反应体系冷却到室温后，旋蒸除去多余的甲苯，然后减压蒸馏，得到最终产物C-12，共5.28g，产率96％。Under a nitrogen atmosphere, 2.70 g (0.01 mol) of fumaric acid (3-ethyl-3-hydroxymethyloxetane) (glycidyl) ester, 3.08 g (0.011 mol) of 1H, 1H, 2H, 2H-perfluorohexyl mercaptan, 0.0328g (0.0002mol) of azobisisobutyronitrile and 10mL of toluene were added to the three-necked flask and mixed well. The reaction mixture was then warmed to 85 ° C and stirred for 8h. After the reaction is completed, after the reaction system is cooled to room temperature, the excess toluene is removed by rotary evaporation, and then distilled under reduced pressure to obtain the final product C-12, a total of 5.28 g, and a yield of 96%.

将2.70g(0.01mol)的富马酸(3-乙基-3-羟甲基氧杂环丁烷)(缩水甘油)酯与3.08g(0.011mol)的1H,1H,2H,2H-全氟己硫醇加入到单口烧杯中混合均匀。然后将其置于紫外灯(产生的辐射波段为300-600nm)下曝光30min，得到最终产物C-12，共5.45g，产率99％。Combine 2.70 g (0.01 mol) fumaric acid (3-ethyl-3-hydroxymethyloxetane) (glycidyl) ester with 3.08 g (0.011 mol) of 1H, 1H, 2H, 2H-full Add fluorohexyl mercaptan to a single-mouth beaker and mix well. It was then exposed to an ultraviolet lamp (with a radiation band of 300-600 nm) for 30 min to obtain the final product C-12, with a total of 5.45 g and a 99% yield.

所得产物的核磁氢谱： ¹H NMR(400MHz,CDCl ₃)δ4.77(dd,J＝12.5,7.0Hz,1H),4.37(d,J＝5.9Hz,2H),4.22(d,J＝6.0Hz,2H),4.11–4.02(m,2H),3.94(s,2H),3.80(td,J＝12.5,2.8Hz,1H),3.24–3.10(m,2H),3.08(td,J＝12.5,3.1Hz,1H),2.84(dd,J＝12.4,7.0Hz,1H),2.74–2.66(m,1H),2.70–2.57(m,1H),2.43(dd,J＝7.0,4.9Hz,1H),2.27–2.11(m,1H),1.69(q,J＝8.0Hz,2H),0.88(t,J＝8.0Hz,3H). Nuclear magnetic hydrogen spectrum of the obtained product: ¹ H NMR (400 MHz, CDCl ₃ ) δ 4.77 (dd, J = 12.5, 7.0 Hz, 1H), 4.37 (d, J = 5.9 Hz, 2H), 4.22 (d, J = 6.0Hz, 2H), 4.11–4.02 (m, 2H), 3.94 (s, 2H), 3.80 (td, J = 12.5, 2.8Hz, 1H), 3.24–3.10 (m, 2H), 3.08 (td, J = 12.5, 3.1Hz, 1H), 2.84 (dd, J = 12.4, 7.0Hz, 1H), 2.74–2.66 (m, 1H), 2.70–2.57 (m, 1H), 2.43 (dd, J = 7.0, 4.9 Hz, 1H), 2.27-2.11 (m, 1H), 1.69 (q, J = 8.0Hz, 2H), 0.88 (t, J = 8.0Hz, 3H).

发明化合物固化成膜：The compound of the invention is cured into a film:

将1g发明化合物与0.01g的光引发剂(如下化合物A)混合。将所得混合物以0.5g/cm ²旋涂于玻璃板上，无需干燥，然后将玻璃板放置于低压汞灯(λ＝365nm处的光照强度P＝30mW/cm ²)下，光照10min使其固化成膜。 1 g of the inventive compound was mixed with 0.01 g of photoinitiator (compound A below). The obtained mixture was spin-coated on a glass plate at 0.5 g / cm ² without drying, and then the glass plate was placed under a low-pressure mercury lamp (light intensity at λ = 365 nm P = 30 mW / cm ² ) and cured by light for 10 minutes Film formation.

为验证单体化合物固化成膜的性质，测该膜的铅笔硬度以及做如下测试：涂膜表面耐指纹性能测试In order to verify the properties of the monomer compound cured into a film, the pencil hardness of the film is measured and the following tests are performed: Fingerprint resistance test of the coating film surface

涂膜表面耐指纹性能的表征方法有接触角和耐油性笔测试2种。接触角采用静态液滴量角法测定，测试温度25℃，湿度50％。耐油性笔测试:取样板中间位置，呈对称标记2个点，2点相距5cm；用油性笔在2点间画一条直线，用无尘布擦拭，记为次数1次；再在同一位置用油性笔画直线并用无尘布擦拭，如此重复直至油性笔迹无法用无尘布擦净，记下次数为N次，则耐油性笔次数为(N-1)次。There are two methods for characterizing the fingerprint resistance of the coating surface: contact angle and oil resistance pen test. The contact angle is determined by the static droplet angle method, with a test temperature of 25 ° C and a humidity of 50%. Oil resistance pen test: the middle position of the sampling plate is marked with two points symmetrically, and the two points are 5cm apart; draw a straight line between the two points with an oil pen, wipe with a dust-free cloth, and record it as the number of times; then use it at the same position Wipe the oily stroke straight and wipe it with a dust-free cloth. Repeat this way until the oily handwriting cannot be wiped off with a dust-free cloth. Write down the number N times, then the number of oil-resistant pens is (N-1).

表面能的测试Surface energy testing

固体与液体接触相间的表面张力可以表述如下式：The surface tension between solid and liquid can be expressed as follows:

式(1)中，In formula (1),

γ _SL为固体与液体接触相间的表面张力，单位为N/m； γ _SL is the surface tension between solid and liquid in contact, the unit is N / m;

分别为固体总表面能、固体表面能的色散分量和固体表面能的极性分量，单位均为N/m；以及

Are the total solid surface energy, the dispersion component of the solid surface energy, and the polar component of the solid surface energy, in N / m; and

分别表示受试液体的总表面能、表面能的色散分量和表面能的极性分量，单位均为N/m。

Respectively represent the total surface energy of the tested liquid, the dispersion component of the surface energy and the polar component of the surface energy, the unit is N / m.

固体和受试液体的总表面能与表面能的色散分量和极性分量分别满足下面两个方程：The total surface energy of the solid and the tested liquid and the dispersion component and polarity component of the surface energy satisfy the following two equations, respectively:

将式(1)带入到杨氏方程中可得到下式(4)The formula (1) is brought into the Young's equation to obtain the following formula (4)

根据式(4)可知，通过测量两种已知液体在固体涂层表面的接触角θ，再利用两种已知液体各自的γ _L、

(受试液体的总表面能、表面能的色散分量、表面能的极性分量)数据，通过方程组可以求解出固体涂层表面的

(固体表面能的色散分量、固体表面能的极性分量)。 According to equation (4), it can be known that by measuring the contact angle θ of two known liquids on the surface of the solid coating, the respective γ _L ,

(The total surface energy of the tested liquid, the dispersion component of the surface energy, and the polar component of the surface energy) The data can be solved by the equations

(The dispersion component of the solid surface energy and the polar component of the solid surface energy).

最后根据式(2)求解出固体涂层的总表面能。Finally, the total surface energy of the solid coating is solved according to equation (2).

具体两种受试液以及相关数据如下表所示：The specific two test solutions and related data are shown in the table below:

涂膜表面耐腐蚀性能测试Corrosion resistance test of coating surface

涂膜表面耐腐蚀性能的表征方法主要为耐碱性测试，因为光固化涂料耐酸性较为突出，一般耐碱性较差。The characterization method of the corrosion resistance of the coating film surface is mainly the alkali resistance test, because the light-cured coating has outstanding acid resistance, and generally has poor alkali resistance.

耐碱性测试：取20％NaOH水溶液，用滴管滴1滴在涂层表面，观察涂层发白的时间。Alkali resistance test: take 20% NaOH aqueous solution, use a dropper to drop 1 drop on the surface of the coating, and observe the time for the coating to whitish.

然而，CN 106187953 A中的化合物A-1至A-14，化合物B-1至B-7，化合物C-1至C-4以及化合物D-1至D-7各自固化获得的涂膜的耐油性笔的次数均未超过40次，远远低于本发明化合物。However, oil resistance of the coating film obtained by curing each of Compounds A-1 to A-14, Compounds B-1 to B-7, Compounds C-1 to C-4 and Compounds D-1 to D-7 in CN 106187953 A The frequency of sex pens did not exceed 40, which was far lower than the compounds of the present invention.

Claims

下式(I)化合物：Compounds of the following formula (I):

其中among them

Y为含有1-10个碳原子、优选2-8个碳原子的直链或支化烷基，该烷基的氢原子基本上全被氟替代，优选该烷基的氢原子的80-100％、优选90-100％被氟替代，更优选Y为含有3-8个碳原子的全氟直链或支化烷基；Y is a linear or branched alkyl group containing 1-10 carbon atoms, preferably 2-8 carbon atoms, the hydrogen atoms of the alkyl group are substantially completely replaced by fluorine, preferably 80-100 of the hydrogen atoms of the alkyl group %, Preferably 90-100%, is replaced by fluorine, and more preferably Y is a perfluoro linear or branched alkyl group containing 3-8 carbon atoms;

Z、Z’相同或不同且各自独立地为-(CH ₂) _p-，其中p为0、1、2或3； Z and Z 'are the same or different and are independently-(CH ₂ ) _p- , where p is 0, 1, 2 or 3;

W、W’相同或不同且各自独立地为-(CH ₂) _q-，其中q为0、1、2或3，前提是同环内的p和q不能同时为0； W and W 'are the same or different and are independently-(CH ₂ ) _q- , where q is 0, 1, 2 or 3, provided that p and q in the same ring cannot be 0 at the same time;

(R ₀) _m为W、O、Z与连接Z和W的碳原子一起构成的环上的m个取代基R ₀，其中m为0、1或2，和R ₀选自C ₁-C ₆烷基和羟基C ₁-C ₆烷基，其中当m为2时，两个R ₀可相同或不同； (R ₀ ) _m is m substituents R ₀ on the ring formed by W, O, Z and the carbon atoms connecting Z and W together, wherein m is 0, 1 or 2, and R _{0 is} selected from C ₁ -C ₆ alkyl and hydroxy C ₁ -C ₆ alkyl, wherein when m is 2, the two R ₀ may be the same or different;

(R ₀’) _m’为W’、O、Z’与连接Z’和W’的碳原子一起构成的环上的m’个取代基R ₀’，其中m’为0、1或2，和R ₀’选自C ₁-C ₆烷基和羟基C ₁-C ₆烷基，其中当m’为2时，两个R ₀’可相同或不同，(R ₀) _m与(R ₀’) _m’相同或不同； (R ₀ ') _m' is m 'substituents R ₀ ' on the ring formed by W ', O, Z' and the carbon atoms connecting Z 'and W', wherein m 'is 0, 1 or 2, And R ₀ 'are selected from C ₁ -C ₆ alkyl and hydroxy C ₁ -C ₆ alkyl, wherein when m' is 2, the two R ₀ 'may be the same or different, (R ₀ ) _m and (R ₀ ') _{m' is the} same or different;

n1、n1’相同或不同且各自独立地为1或2；n1, n1 'are the same or different and are independently 1 or 2;

n3为1、2、3或4；n3 is 1, 2, 3 or 4;

R ₁、R ₂、R ₁’和R ₂’各自独立地选自H、C ₁-C ₆烷基和C ₁-C ₆烷氧基，当n1为2时，两个R ₁可相同或不同，和两个R ₂可相同或不同，当n1’为2时，两个R ₁’可相同或不同，和两个R ₂’可相同或不同；以及 R ₁ , R ₂ , R ₁ 'and R ₂ ' are each independently selected from H, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy, when n1 is 2, the two R ₁ may be the same or Different, and two R ₂ may be the same or different, when n1 'is 2, two R ₁ ' may be the same or different, and two R ₂ 'may be the same or different; and

R ₅和R ₆各自独立地选自H和C ₁-C ₆烷基，其中当n3为2、3或4时，n3个R ₅可相同或不同，和n3个R ₆可相同或不同。 R ₅ and R ₆ are each independently selected from H and C ₁ -C ₆ alkyl, wherein when n 3 is 2, 3 or 4, n 3 R ₅ may be the same or different, and n 3 R ₆ may be the same or different.
如权利要求1所述的化合物，其中同环内的p和q均为1，或者同环内的p和q中之一为0，另一为1。The compound according to claim 1, wherein p and q in the same ring are both 1, or one of p and q in the same ring is 0, and the other is 1.
如权利要求1或2所述的化合物，其中m为0或1，当m为1时，R ₀优选位于连接Z和W的碳原子上；和/或，m’为0或1，当m’为1时，R _0’优选位于连接Z’和W’的碳原子上。 The compound according to claim 1 or 2, wherein m is 0 or 1, when m is 1, R ₀ is preferably located on the carbon atom connecting Z and W; and / or, m ′ is 0 or 1, when m When 'is 1, R _0' is preferably located on the carbon atom connecting Z 'and W'.
如权利要求1-3中任一项所述的化合物，其中n1和/或n1’为1；和/或，n3为2。The compound according to any one of claims 1 to 3, wherein n1 and / or n1 'is 1; and / or n3 is 2.
如权利要求1-4中任一项的化合物，其中The compound according to any one of claims 1 to 4, wherein

R ₀和R ₀’相同或不同且独立地选自C ₁-C ₄烷基和羟基C ₁-C ₄烷基；和/或 R ₀ and R ₀ 'are the same or different and are independently selected from C ₁ -C ₄ alkyl and hydroxy C ₁ -C ₄ alkyl; and / or

R ₁、R ₂、R ₁’和R ₂’各自独立地选自H、C ₁-C ₄烷基和C ₁-C ₄烷氧基，优选R ₁、R ₂、R ₁’和R ₂’均为H；和/或 R ₁ , R ₂ , R ₁ ′ and R ₂ ′ are each independently selected from H, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, preferably R ₁ , R ₂ , R ₁ ′ and R ₂ 'All H; and / or

R ₅和R ₆各自独立地选自H和C ₁-C ₄烷基，优选均为H。 R ₅ and R ₆ are each independently selected from H and C ₁ -C ₄ alkyl, preferably both are H.
如权利要求1-5中任一项的化合物，其中Z与Z’相同，W与W’相同，(R ₀) _m与(R ₀’) _m’相同，n1与n1’相同，R ₁与R ₁’相同，以及R ₂与R ₂’相同。 The compound according to any one of claims 1 to 5, wherein Z is the same as Z ', W is the same as W', (R ₀ ) _{m is the} same as (R ₀ ') _m' , n1 is the same as n1 ', R ₁ is R ₁ 'is the same, and R _{2 is the} same as R ₂ '.
如权利要求1的化合物，其为选自下组的化合物：The compound according to claim 1, which is a compound selected from the group consisting of:
一种制备如权利要求1-7中任一项所述的式(I)化合物的方法，包括：A method for preparing the compound of formula (I) according to any one of claims 1-7, comprising:

1)使式(II)化合物1) The compound of formula (II)

其中X和X’相同或不同且各自独立地为卤素，优选氯或溴；Where X and X 'are the same or different and are each independently halogen, preferably chlorine or bromine;

与式(III)化合物进行酯化反应或与式(III)化合物和式(III’)化合物先后进行酯化反应，Performing an esterification reaction with a compound of formula (III) or successively performing an esterification reaction with a compound of formula (III) and a compound of formula (III ’),

其中Z、Z’、W、W’、R ₀、R ₀’、R ₁、R ₁’、R ₂、R ₂’、m、m’、n1和n1’如对式(I)化合物所定义， Where Z, Z ', W, W', R ₀ , R ₀ ', R ₁ , R ₁ ', R ₂ , R ₂ ', m, m', n1 and n1 'are as defined for the compound of formula (I) ,

得到式(IV)化合物，The compound of formula (IV) is obtained,

其中Z、Z’、W、W’、R ₀、R ₀’、R ₁、R ₁’、R ₂、R ₂’、m、m’、n1和n1’如对式(I)化合物所定义；以及 Where Z, Z ', W, W', R ₀ , R ₀ ', R ₁ , R ₁ ', R ₂ , R ₂ ', m, m', n1 and n1 'are as defined for the compound of formula (I) ;as well as

2)使式(IV)化合物与式(V)化合物反应，2) React the compound of formula (IV) with the compound of formula (V),

其中R ₅、R ₆、n3和Y如对式(I)化合物所定义， Where R ₅ , R ₆ , n3 and Y are as defined for the compound of formula (I),

得到式(I)化合物。The compound of formula (I) is obtained.
如权利要求8所述的方法，其中步骤1)中的反应在俘酸剂存在下进行，优选俘酸剂为三乙胺、苯胺、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾或其任意混合物。The method according to claim 8, wherein the reaction in step 1) is carried out in the presence of an acid trapping agent, preferably the acid trapping agent is triethylamine, aniline, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or the like Any mixture.
如权利要求8或9所述的方法，其中当式(II)化合物与仅仅式(III)化合物进行酯化反应时(即Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’每组各自相同时)，式(III)化合物与式(II)化合物的摩尔比为2.0-3.0，优选为2.1-2.5；当式(II)化合物与式(III)化合物和式(III’)化合物先后进行酯化反应时(即Z与Z’、W与W’、R ₀与R ₀’、R ₁与R ₁’、R ₂与R ₂’、m与m’和n1与n1’这几组中至少一组不同时)，式(III)化合物和式(III’)化合物各自与式(II)化合物的摩尔比为1.0-2.0，优选为1.1-1.5；和/或，俘酸剂与式(II)化合物的摩尔比为2.0-3.0，优选为2.1-2.5；和/或，步骤1)中的反应在20-30℃的温度下进行，优选在室温下进行。 The method according to claim 8 or 9, wherein when the compound of formula (II) and only the compound of formula (III) undergo an esterification reaction (ie Z and Z ', W and W', R ₀ and R ₀ ', R ₁ and R ₁ ', R ₂ and R ₂ ', m and m 'and n1 and n1' are the same for each group), the molar ratio of the compound of formula (III) to the compound of formula (II) is 2.0-3.0, preferably is 2.1-2.5; When the compound of formula (II), the compound of formula (III) and the compound of formula (III ') are successively subjected to an esterification reaction (ie Z and Z', W and W ', R ₀ and R ₀ ', R ₁ Different from at least one of the groups R ₁ ', R ₂ and R ₂ ', m and m ', and n1 and n1'), the compound of formula (III) and the compound of formula (III ') are each different from formula (II) The molar ratio of the compound is 1.0-2.0, preferably 1.1-1.5; and / or, the molar ratio of the acid trapping agent to the compound of formula (II) is 2.0-3.0, preferably 2.1-2.5; and / or, in step 1) The reaction is carried out at a temperature of 20-30 ° C, preferably at room temperature.
如权利要求8-11中任一项所述的方法，其中步骤2)的反应按照步骤2a)进行：2a)在自由基引发剂存在下和在无氧气的条件下，使式(IV)化合物与式(V)化合物进行反应，优选的是，The method according to any one of claims 8 to 11, wherein the reaction of step 2) is carried out according to step 2a): 2a) in the presence of a radical initiator and in the absence of oxygen, the compound of formula (IV) React with the compound of formula (V), preferably,

所述自由基引发剂选自偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过氧化二苯甲酰或其任意混合物；和/或，式(IV)化合物与式(V)化合物的摩尔比为0.8-1.5，优选0.9-1.1；和/或，步骤2a)的反应在40-110℃，优选50-100℃的温度下进行。The free radical initiator is selected from azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide or any mixture thereof; and / or, formula (IV ) The molar ratio of the compound to the compound of formula (V) is 0.8-1.5, preferably 0.9-1.1; and / or the reaction of step 2a) is carried out at a temperature of 40-110 ° C, preferably 50-100 ° C.
如权利要求8-11中任一项所述的方法，其中步骤2)的反应按照步骤2b)进行：2b)使式(IV)化合物和式(V)化合物在紫外光照射下反应，优选的是，The method according to any one of claims 8-11, wherein the reaction of step 2) is carried out according to step 2b): 2b) The compound of formula (IV) and the compound of formula (V) are reacted under ultraviolet light irradiation, preferably Yes,

步骤2b)的反应在发射波段为300-600nm的紫外灯照射下进行；和/或，式(IV)化合物与式(V)化合物的摩尔比为0.8-1.5，优选0.9-1.0；和/或，步骤2b)的反应在室温下进行。The reaction of step 2b) is carried out under the irradiation of an ultraviolet lamp with an emission band of 300-600 nm; and / or, the molar ratio of the compound of formula (IV) to the compound of formula (V) is 0.8-1.5, preferably 0.9-1.0; and / or The reaction of step 2b) is carried out at room temperature.
一种聚合物，其通过将如权利要求1-7中任一项所述的式(I)化合物通过开环聚合而得到，优选通过阳离子光固化开环聚合而得到，该阳离子光固化开环聚合尤其是在光引发剂存在下进行紫外光固化而实现。A polymer obtained by ring-opening polymerization of a compound of formula (I) according to any one of claims 1-7, preferably by cationic photo-curing ring-opening polymerization, the cationic photo-curing ring-opening The polymerization is achieved especially by ultraviolet curing in the presence of a photoinitiator.
一种可光固化组合物，包含如权利要求1-7中任一项所述的式(I)化合物作为聚合单体。A photocurable composition comprising the compound of formula (I) according to any one of claims 1-7 as a polymerizable monomer.
一种光固化材料，该材料通过将根据权利要求14的可光固化组合物光固化而获得。A photocurable material obtained by photocuring the photocurable composition according to claim 14.