Preparation method of cycloolefin polymer

Abstract

The invention discloses a preparation method of a cycloolefin polymer, which comprises the following steps: S1, addition reaction: in an inert atmosphere, dissolving dicyclopentadiene and a polymer with a double bond in a main chain in a solvent, heating to 130-220 DEG C, and carrying out DA addition reaction to obtain an intermediate product with an alicyclic structure introduced into the main chain; s2, hydrogenation reaction: carrying out hydrogenation reaction on the intermediate product obtained in the step S1 and hydrogen under the action of a hydrogenation catalyst to prepare the cycloolefin polymer. The method has the characteristics that the naphthenic base content can be adjusted in a wider range, the product toughness is better at the same glass transition temperature, and the production cost is reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of polyolefin materials, and particularly relates to a preparation method of a cyclic olefin polymer. BACKGROUND

[0002] The cyclic olefin polymer is a non-crystalline transparent polymer with a high molecular main chain and a high steric hindrance cyclic alkane structure, which has high transparency, low birefringence, high water barrier, low water absorption, high purity and excellent electrical properties, and thus becomes a core material in the fields of lenses, lenses, vehicle lamp lenses, screen displays, high-end medical drug / vaccine storage, and has an irreplaceable position in the fields of optics, display, medical treatment and electronics which have high requirements on material performance.

[0003] According to different synthesis routes, commercially available cyclic olefin polymers are mainly divided into two categories: one is ethylene-cyclic olefin addition polymer (referred to as COC); the other is a polymer obtained by ring-opening metathesis polymerization of cyclic olefin followed by hydrogenation (referred to as COP). However, whether COC or COP is prepared, expensive cyclic olefin monomers such as norbornene and tetracyclododecene need to be used as raw materials, which directly leads to high production cost of cyclic olefin polymer products and high price, which limits its wider application to some extent.

[0004] In the process of preparing COC by ethylene-cyclic olefin addition route, the existing technology usually adjusts the performance of the product by adjusting the ratio of cyclic olefin and ethylene monomers, and some related technical materials disclose that the performance of the product can be adjusted by introducing styrene and other third monomers. However, due to the large difference in reactivity between cyclic olefin monomers and ethylene, styrene and other monomers, the above performance adjustment method can only be realized within a small range, and the adjustment effect is limited; at the same time, the difference in reactivity is also easy to cause the cyclic olefin monomers to form repeated chain units, and then cause the product toughness to deteriorate and other problems, affecting the use performance of the product.

[0005] In the process of preparing COP by ring-opening metathesis polymerization-hydrogenation route of cyclic olefin, the existing technology has a single means of adjusting the performance of the product, and at present can only rely on the design and use of cyclic olefin monomers with different structures to achieve it, which cannot meet the diversified performance requirements of COP products in different application scenarios, further limiting the application expansion of COP products.

[0006] In summary, the existing preparation method of cyclic olefin polymer has problems such as high raw material cost, narrow performance adjustment range or single adjustment means, and easy to produce performance defects, and a new cyclic olefin polymer preparation technology needs to be developed to solve the above problems in the existing technology. SUMMARY

[0007] To solve the above technical problems, the present application provides a preparation method of cyclic olefin polymer.

[0008] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0009] A preparation method of cyclic olefin polymer, comprising the following steps:

[0010] S1, addition reaction: under inert atmosphere, dicyclopentadiene and main chain double bond-containing polymer are dissolved in a solvent, heated to 130-220℃ to occur DA addition reaction, to obtain an intermediate product with aliphatic ring structure introduced into the main chain;

[0011] S2, hydrogenation reaction: the intermediate product obtained in step S1 is subjected to hydrogenation reaction with hydrogen under the action of hydrogenation catalyst, to prepare cyclic olefin polymer.

[0012] As a preferred example of the present application, in the main chain double bond-containing polymer, the existence form of double bond structure comprises at least one of , wherein * represents the connection site with the polymer chain segment, and n has a value of 1 or 2;

[0013] Preferably, the double bond content in the main chain double bond-containing polymer is 2-20 mmol / g, preferably 10-20 mmol / g.

[0014] As a preferred example of the present application, the main chain double bond-containing polymer is selected from one or more of polybutadiene, polyisoprene, styrene butadiene rubber, and styrene thermoplastic elastomer;

[0015] Preferably, the weight average molecular weight of the main chain double bond-containing polymer is 10000-110000, preferably 10000-55000.

[0016] As a preferred example of the present application, in step S1, the molar ratio of dicyclopentadiene to double bond in the main chain double bond-containing polymer is 0.1-1.1, preferably 0.1-0.6.

[0017] As a preferred example of the present application, in step S1, the solvent is selected from at least one of aliphatic hydrocarbon solvent, alicyclic hydrocarbon solvent, aromatic hydrocarbon solvent, halogenated aromatic hydrocarbon solvent, and ether solvent;

[0018] Preferably, the aliphatic hydrocarbon solvent is selected from at least one of n-hexane and heptane;

[0019] Preferably, the alicyclic hydrocarbon solvent is selected from at least one of cyclopentane, cyclohexane, methylcyclohexane, and dimethylcyclohexane;

[0020] Preferably, the aromatic hydrocarbon solvent is selected from at least one of benzene, toluene, and xylene;

[0021] Preferably, the halogenated aromatic hydrocarbon solvent is selected from at least one of chlorobenzene, dichlorobenzene;

[0022] Preferably, the ether solvent is selected from at least one of diethyl ether, tetrahydrofuran;

[0023] Preferably, the amount of the solvent added in step S1 is 1-10 times, preferably 2-4 times, the mass of the main chain double bond-containing polymer;

[0024] Preferably, the reaction time in step S1 is 0.5-5h, preferably 1-3h.

[0025] In the present application, step S1 can also optionally add antioxidants, polymerization inhibitors and other substances to inhibit crosslinking, oxidation and other side reactions, and the reaction form can be batch tank reaction or continuous reaction according to engineering requirements; the present application does not make specific limitations.

[0026] As a preferred example of the present application, the hydrogenation catalyst is a homogeneous catalyst or a heterogeneous catalyst, which can be selected according to conventional methods in the field, and the present application does not have special requirements.

[0027] The homogeneous catalyst is selected from at least one of soluble complexes of metals nickel, titanium, palladium, platinum, rhodium, ruthenium or a catalyst system thereof, preferably at least one of Ziegler hydrogenation catalysts composed of nickel salt-alkyl aluminum, titanium metallocene-alkyllithium hydrogenation catalysts, Ru complex catalysts;

[0028] The heterogeneous catalyst is selected from at least one of metal-loaded silica, metal-loaded alumina, metal-loaded titanium oxide, and skeletal nickel; the metal is selected from at least one of nickel, palladium, platinum, rhodium, and ruthenium.

[0029] As a preferred example of the present application, the amount of the hydrogenation catalyst added is 0.001-10% of the mass of the reaction solution obtained in step S1.

[0030] As a preferred example of the present application, the hydrogenation reaction temperature in step S2 is 60-200℃, and the reaction pressure is 1-7MPa.

[0031] As a preferred example of the present application, after the hydrogenation reaction in step S2, the residual amount of double bonds in the polymer is 0.05-1mmol / g.

[0032] In the present application, the reaction form in step S2 can be batch tank reaction or continuous reaction according to engineering requirements; the present application does not make specific limitations.

[0033] The present application has the following beneficial effects:

[0034] 1. Significantly reduce raw material cost, improve product economy: The present application discards the expensive cycloalkene monomers such as norbornene, tetracyclododecene, etc. that must be used in the existing cycloalkene polymer preparation process, and uses cheap and readily available main chain double bond containing polymer and dicyclopentadiene as core raw materials, which greatly reduces the production cost of cycloalkene polymer from the source, effectively solves the problem of high product price and limited application, and is more conducive to promoting the wide application of cycloalkene polymer in various fields.

[0035] 2. Realize wide range of performance adjustment and adapt to diversified needs: The present application can quantitatively introduce alicyclic structure into the polymer main chain by controlling the addition reaction degree of the main chain double bond containing polymer and dicyclopentadiene, and then obtain cycloalkene polymers with different alicyclic content and alicyclic structure. This adjustment method breaks through the limitations of narrow performance adjustment range and single performance adjustment means of existing cycloalkene polymers, and can realize precise control of polymer performance in a wide range, and can flexibly adapt to the diversified needs of materials performance in different fields such as optics, display, medical treatment and electronics.

[0036] 3. Optimize core performance of products and improve use value: The cycloalkene polymer obtained by the addition reaction of the polymer with at least one vinyl group between the main chain double bonds and dicyclopentadiene significantly improves the toughness of the product while maintaining the core excellent properties of the existing cycloalkene polymer such as high heat resistance, high modulus and high transparency. Specifically, the product has better toughness at the same glass transition temperature (Tg), or the Tg of the product is significantly improved at the same toughness level, effectively solving the toughness degradation problem caused by the formation of cycloalkene monomer repeating unit in the existing adjustment method, and further improving the use performance and application reliability of cycloalkene polymer.

[0037] 4. Preparation process is flexible and controllable, and has industrialization potential: The preparation process of the present application introduces alicyclic structure by addition reaction, and then obtains saturated cycloalkene polymer hydride by hydrogenation, which has clear reaction path and strong controllability. Compared with the process instability problem caused by the difference in monomer reactivity ratio in the existing preparation method, and the limitation of single design of monomer structure, the process route of the present application is more flexible and operable, and is convenient for industrialization scale-up production. DETAILED DESCRIPTION

[0038] The present application will be further described below through specific examples, and the examples described in the present application are only used to illustrate the present application and do not limit the scope of the present application.

[0039] The raw materials used in the examples are all conventional raw materials in the art, and the purity specifications used are analytical pure or chemical pure.

[0040] The source information of raw materials used in the following examples is as follows, and other raw materials are conventional raw materials in the art, and the purity specifications used are analytical or chemical purity:

[0041] Cyclohexane: 99%, Luxi Chemical Co., Ltd.;

[0042] Dicyclopentadiene (DCPD): 98% (GC), Sigma-Aldrich;

[0043] Butadiene: 99.999%, Dalian Guangming Special Gas Co., Ltd.;

[0044] Styrene: 99%, Shanghai Aldrin;

[0045] n-Butyllithium: 2.5 mol / L hexane solution, Shanghai Aldrin;

[0046] High-purity hydrogen: 99.999%, Dalian Guangming Special Gas Co., Ltd.;

[0047] Nickel acetylacetonate (Ni(acac)2): 95%, Shanghai Aldrin;

[0048] Triisobutylaluminum (TIBA): 1.0 mol / L n-hexane solution, Shanghai Aldrin;

[0049] Supported nickel catalyst: 65wt% Ni@Al2O3, Shanghai Aldrin;

[0050] ZEONEX K26R, cyclic olefin polymer, ZEON Corporation;

[0051] APEL 5014, cyclic olefin polymer, Mitsui Chemicals;

[0052] Topas 6013, cyclic olefin polymer, Topas Advanced Polymers;

[0053] Topas 8007, cyclic olefin polymer, Topas Advanced Polymers.

[0054] The performance test parameters and corresponding test methods used in each embodiment of the present application are as follows:

[0055] The structure of the compounds and polymers synthesized in the present application is measured by a Brucker ARX-400 nuclear magnetic resonance instrument, with deuterated chloroform (CDCl3), deuterated benzene (C6D6), deuterated cyclohexane (C6D 12 ), deuterated 1,1,2,2-tetrachloroethane (C2D2Cl4) as the solvent, and the measurement is carried out at room temperature or 90°C.

[0056] The weight average molecular weight (Mw) and the molecular weight distribution (PDI) of the polymer synthesized in the present application are obtained by PL-GPC220 at 150℃, using three PL gel 10 μm MIXED-B separation columns connected in series, 1,2,4-trichlorobenzene as solvent, 1 ml / min, polystyrene narrow distribution standard sample.

[0057] The thermal performance (Tg) of the polymer is determined by TA Q2000 type differential scanning calorimeter according to ISO 11357 standard;

[0058] The refractive index and light transmittance of the polymer are measured by Ataog DR-M4 refractometer according to ASTM-D542 standard;

[0059] The elongation at break and tensile modulus of the polymer are tested by standard dumbbell-shaped sample (total length 170 mm, narrow part width 10 mm, thickness 4 mm) according to ISO 527 standard.

[0060] Unless otherwise specified, the pressure in the following embodiments of the present application refers to gauge pressure.

[0061]

Preparation Example

[0062] (1) Preparation of Polymer-1: A 10 L stainless steel reactor is heated to replace the inside of the kettle with a dry and anaerobic environment, and then cooled to room temperature. A certain amount of cyclohexane 4000 g and butadiene 1600 g are added into the kettle, and the kettle is pressurized to 1 MPa. The heating is turned on and the reaction temperature is preheated. 59 mL of initiator n-butyllithium is added to initiate the reaction. The polymerization reaction liquid is obtained by reacting at 50℃ for 60 min. Ethanol is added to the reaction liquid to precipitate and wash the solid precipitate, and then dried to obtain the backbone containing double bond polymer.

[0063] (2) Preparation of Polymer-2 to Polymer-7: The operation is the same as that of Polymer-1, except that the amount of solvent, cyclohexane, monomer and initiator added into the kettle is different, and the addition conditions are shown in Table 1 below.

[0064] Table 1

[0065]

[0066]

[0067] 3) Preparation of Polymer-8: A 10L stainless steel reactor was heated to replace the inside of the kettle with a dry and oxygen-free environment, and then cooled to room temperature. A certain amount of cyclohexane 4000g and butadiene 450g were added to the kettle, and the kettle was pressurized to 1MPa. Heating was started, and the temperature was preheated to the reaction temperature. 10mL of initiator n-butyllithium was added to initiate the reaction. After 30min of reaction at 50℃, 700g of styrene was added to the reaction kettle, and the reaction was continued for another 30min. Then 450g of butadiene was added to the kettle and reacted for 30min to obtain a polymerization reaction solution. Ethanol was added to the reaction solution to precipitate and wash the solid precipitate, and then dried to obtain a polymer containing double bonds in the main chain.

[0068] The product indicators were analyzed as shown in Table 2.

[0069] Table 2

[0070]

[0071]

[0072] Example 1

[0073] A method for preparing a cyclic olefin polymer, comprising the following steps:

[0074] S1, addition reaction:

[0075] Under an inert atmosphere, 122g of dicyclopentadiene was dissolved in 2000g of toluene with 500g of Polymer-1 (the molar ratio of dicyclopentadiene to double bonds in Polymer-1 was 0.1). The mixture was heated to 140℃ and reacted for 3h. Then the reaction solution was cooled, ethanol was added to precipitate and wash the solid precipitate, and Polymer-1D was obtained.

[0076] S2, hydrogenation reaction:

[0077] A 5L stainless steel kettle reactor was heated to replace the inside of the kettle with a dry and oxygen-free environment, and then cooled to room temperature. The atmosphere in the kettle was replaced with hydrogen gas. 500g of Polymer-1D, 2000g of solvent cyclohexane, and 10g of hydrogenation catalyst supported nickel were added to the reactor. The stirring was started, and the kettle was filled with hydrogen gas to a pressure of 1 / 2 of the reaction pressure. The heating was started, and the temperature was preheated to the reaction temperature of 150℃. Then the hydrogen gas was added to the reaction pressure of 4MPa, and the reaction was continued for 5h. Activated carbon was added to adsorb impurities, and then filtered and separated. Ethanol was added to precipitate and wash the solid precipitate, and then dried to obtain a cyclic olefin polymer.

[0078] The cycloalkyl content, Mw, PDI, and other physical indicators of the cyclic olefin polymer obtained in this example are shown in Table 5.

[0079] Examples 2-12

[0080] The cycloolefin polymers were prepared in a substantially same manner as in Example 1, except that the reaction conditions in different examples were adjusted as shown in Table 3, Table 4.

[0081] The cycloalkyl content, Mw, PDI and other physical properties of the cycloolefin polymers obtained in different examples are shown in Table 5.

[0082] Table 3, addition reaction conditions in different examples

[0083]

[0084]

[0085] Table 4, hydrogenation reaction conditions in different examples

[0086]

[0087]

[0088] Note: The catalyst system of Ni(acac)2+TIBA was prepared in advance as follows: in a glove box, 484 ml of cyclohexane was added to a 1000 ml round bottom flask, stirring was started, 1.028 g (4 mmol) of Ni(acac)2 was weighed and dispersed in cyclohexane, 16 ml (16 mmol) of TIBA was added dropwise into the flask, after the dropwise addition was completed, stirring was continued for 15 min, and a hydrogenation catalyst solution was obtained; the amount of the hydrogenation catalyst added in the examples in Table 4 was based on the mass of Ni in the catalyst system.

[0089] In addition, the cycloolefin polymers provided in different examples were injection molded into test bars according to the following method, and the Tg, refractive index, light transmittance, tensile modulus, elongation at break and other properties were tested, as shown in Table 5.

[0090] The injection molding method was as follows: the plasticizing temperature of the extruder was 270-290°C, the screw rotation speed was 10-100 rpm, the back pressure was 3-10 MPa, the forward speed of the screw was 2-100 mm / s, and the holding pressure time was 5-15 s.

[0091] Table 5, related test indexes of the cycloolefin polymers

[0092]

[0093]

[0094] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and supplements without departing from the method of the present application, and these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. A method for preparing a cyclic olefin polymer, characterized in that, Includes the following steps: S1. Addition reaction: Under an inert atmosphere, dicyclopentadiene and a polymer containing double bonds in the main chain are dissolved in a solvent and heated to 130-220℃ to undergo a DA addition reaction, obtaining an intermediate product that introduces an alicyclic structure into the main chain. S2, Hydrogenation reaction: The intermediate product obtained in step S1 is hydrogenated with hydrogen in the presence of a hydrogenation catalyst to obtain a cyclic olefin polymer.

2. The method for preparing the cyclic olefin polymer according to claim 1, characterized in that, In the polymer containing double bonds in the main chain, the forms in which the double bond structure exists include: At least one of them, wherein * represents the connection site with the polymer repeating segment, and n takes the value of 1 or 2; Preferably, the double bond content in the main chain polymer is 2-20 mmol / g, more preferably 10-20 mmol / g.

3. The method for preparing the cyclic olefin polymer according to claim 2, characterized in that, The polymer containing double bonds in the main chain is selected from one or more of polybutadiene, polyisoprene, styrene-butadiene rubber, and styrene thermoplastic elastomers. Preferably, the weight-average molecular weight of the polymer containing double bonds in the main chain is 10,000-110,000, more preferably 10,000-55,000.

4. The method for preparing the cyclic olefin polymer according to any one of claims 1-3, characterized in that, In step S1, the molar ratio of dicyclopentadiene to the double bonds in the main chain of the polymer containing double bonds is 0.1-1.1, preferably 0.1-0.

6.

5. The method for preparing the cyclic olefin polymer according to any one of claims 1-4, characterized in that, The solvent mentioned in step S1 is selected from at least one of aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, and ether solvents; Preferably, the amount of solvent added in step S1 is 1-10 times the mass of the main chain polymer containing double bonds, more preferably 2-4 times.

6. The method for preparing the cyclic olefin polymer according to any one of claims 1-5, characterized in that, The hydrogenation catalyst is a homogeneous catalyst or a heterogeneous catalyst; The homogeneous catalyst is selected from at least one soluble complex of nickel, titanium, palladium, platinum, rhodium, and ruthenium or its catalyst system, preferably selected from at least one of the following: a Ziegler hydrogenation catalyst composed of nickel salt and alkylaluminum, a titanium locene-alkyllithium hydrogenation catalyst, and a Ru-based complex catalyst. The heterogeneous catalyst is selected from at least one of metal-supported silica, metal-supported alumina, metal-supported titanium dioxide, and skeletal nickel; the metal is selected from at least one of nickel, palladium, platinum, rhodium, and ruthenium.

7. The method for preparing the cyclic olefin polymer according to any one of claims 1-6, characterized in that, The amount of hydrogenation catalyst added is 0.001-10% of the mass of the reaction solution obtained in step S1.

8. The method for preparing the cyclic olefin polymer according to any one of claims 1-7, characterized in that, In step S2, the hydrogenation reaction temperature is 60-200℃ and the reaction pressure is 1-7MPa.

9. The method for preparing the cyclic olefin polymer according to any one of claims 1-8, characterized in that, After the hydrogenation reaction in step S2, the residual amount of double bonds in the polymer is 0.05-1 mmol / g.

Images