Cycloolefin monomer composition, hydrogenated polymer as well as preparation method and application of hydrogenated polymer

Abstract

The invention discloses a cycloolefin monomer composition. The cycloolefin monomer composition comprises the following components in percentage by mass: 0.001 wt% to 25 wt% of a norbornene derivative and 75 wt% to 99.999 wt% of polycycloolefin, the norbornene derivative comprises one or more of compounds as shown in formulas (1)-(4). According to the present invention, the cycloolefin monomer composition is subjected to ring opening polymerization and then hydrogenation to obtain the hydrogenated polymer, and the norbornene derivative ring opening group is introduced, such that the ductility and the transparency of the hydrogenated polymer can be effectively improved, the elongation at break can achieve 450%, the light transmittance can achieve 94.1%, the haze is as low as 0.2%, and the broad application prospect is provided.

Description

Technical Field

[0001] The present application relates to the field of cycloolefin ring-opening hydrogenated polymers, and in particular to a cycloolefin monomer composition, a hydrogenated polymer, and a preparation method and application thereof. Background Art

[0002] Cyclic olefin copolymer is a polymer material with the characteristics of high transparency, low birefringence, low water absorption, high rigidity, high heat resistance, high refractive index, and good water vapor airtightness. It is used for medical optical components and high-end pharmaceutical packaging materials. It is an amorphous thermoplastic polymer material that has attracted great attention in industry and academia in recent years. It has broad application prospects in optics, electronics, pharmaceutical packaging and other fields.

[0003] At present, the insufficient ductility of cycloolefin copolymer materials limits their application. CN113557258A discloses a hydrogenated ring-opening polymer containing a structural unit derived from norbornene in a specified proportion or more and having specified properties, which has excellent ductility but poor transparency and limited application areas.

[0004] Therefore, providing a monomer composition for preparing a hydrogenated polymer having ductility and transparency is a problem to be solved by those skilled in the art. Summary of the invention

[0005] In view of this, the present application provides a cycloolefin monomer composition for preparing a hydrogenated polymer, and introduces a specific norbornene derivative structural unit into the cycloolefin copolymer, which can not only improve the ductility, but also make the transparency of the polymer more excellent, and has better comprehensive performance.

[0006] The present application provides a cycloolefin monomer composition, which comprises, by weight percentage: 0.001 wt % to 25 wt % of a norbornene derivative and 75 wt % to 99.999 wt % of a polycyclic olefin;

[0007] The norbornene derivatives include one or more compounds represented by formula (1) to formula (4);

[0008]

[0009]

[0010] The present application uses norbornene derivatives and polycyclic olefins as raw materials to prepare hydrogenated polymers. The norbornene derivatives include but are not limited to one or more of the compounds shown in formula (1) to formula (4), and contain phenyl and norbornene groups. The present application has no special requirements for the selection of norbornene derivatives. In some specific implementations, the mass percentage of the norbornene derivative is 0.1wt% to 24wt%, preferably 15wt% to 22.5wt%. In some specific implementations, the cycloolefin monomer composition includes 0% to 10% of the compound shown in formula (1), 0% to 25% of the compound shown in formula (2), 0% to 25% of the compound shown in formula (3) and 0% to 25% of the compound shown in formula (3); the compounds shown in formula (1) to formula (4) are not 0 at the same time, and the total mass percentage of the compounds shown in formula (1) to formula (4) does not exceed 25%. In some specific implementations, the cycloolefin monomer composition is a compound represented by formula (1), and its mass percentage content is 0.001% to 10%, preferably 2% to 8%, and more preferably 5% to 7.5%. In some specific implementations, the cycloolefin monomer composition is one or more of the compounds represented by formula (2), formula (3), and formula (4), and its mass percentage content is 0.001% to 25%, preferably 5% to 20%, and more preferably 10% to 15%. In some specific implementations, the cycloolefin monomer composition is one or more of the compounds represented by formula (1), formula (2), formula (3), and formula (4), and the mass percentage content of the norbornene derivative is 0.001% to 25%, preferably 5% to 20%, and more preferably 10% to 15%, wherein the mass percentage content of the compound represented by formula (1) is 0% to 10%, preferably 2% to 8%, and more preferably 5% to 7.5%.

[0011] In some specific implementations, the polycyclic olefin includes, but is not limited to, one or more of dicyclopentadiene, tricyclopentadiene, norbornene, methyl norbornene, ethylidene norbornene, or tetracyclododecene, and any olefin containing a polycyclic structure that can undergo ring-opening polymerization is sufficient. The present application has no special requirements for the selection of polycyclic olefins. In some specific implementations, the mass percentage of the polycyclic olefin is 80wt% to 99.999wt%, preferably 87.5wt% to 99.999wt%.

[0012] The present application also provides a hydrogenated polymer, which is prepared using the above cycloolefin monomer composition as a raw material.

[0013] In some specific implementations, the number average molecular weight of the hydrogenated polymer is 50000 to 60000, preferably 53000 to 57000. In some specific implementations, the mass percentage of the phenyl norbornene structural unit in the hydrogenated polymer is 0.001% to 25%, preferably 5% to 20%, and the mass percentage of the polycyclic olefin structural unit is 80% to 99.999%, preferably 87.5% to 99.999%.

[0014] The present application also provides a method for preparing a hydrogenated polymer, comprising:

[0015] The cycloolefin monomer composition is subjected to a ring-opening polymerization reaction to obtain a ring-opening polymer;

[0016] The ring-opening polymer is subjected to a hydrogenation reaction to obtain a hydrogenated polymer.

[0017] The present application first performs a ring-opening polymerization reaction on the cycloolefin monomer composition to obtain a ring-opening polymer. In some specific implementations, the polymerization reaction is carried out under the catalysis of a catalyst, and the catalyst includes but is not limited to Grubbs2. The present application has no special requirements for the selection of the catalyst. In some specific implementations, the polymerization reaction temperature is 45°C to 65°C, preferably 50°C to 55°C. In some specific implementations, the stirring rate of the ring-opening polymerization reaction is 500rpm to 600rpm.

[0018] The application then carries out a hydrogenation reaction on the obtained polymer to obtain a hydrogenated polymer. In some specific implementations, the hydrogenation reaction is carried out under the catalysis of a catalyst, and the catalyst includes but is not limited to palladium carbon, and the application has no special requirements for the selection of catalysts. In some specific implementations, the temperature of the hydrogenation reaction is 55°C to 65°C, preferably 60°C. In some specific implementations, the pressure of the hydrogenation reaction is 4MPa to 6MPa, preferably 5MPa. In some specific implementations, the time of the hydrogenation reaction is 6h to 9h, preferably 7h to 8h. In some specific implementations, the stirring rate of the hydrogenation reaction is 500rpm to 600rpm.

[0019] The present application also provides a film prepared from the above hydrogenated polymer.

[0020] The present application also provides an optical lens, which is prepared from the above-mentioned hydrogenated polymer.

[0021] The present application also provides an application of a hydrogenated polymer in the preparation of packaging materials.

[0022] In some specific implementations, the packaging material includes but is not limited to medical packaging material.

[0023] The cycloolefin monomer composition provided in the present application comprises, by mass percentage, 0.001wt% to 25wt% of norbornene derivatives and 75wt% to 99.999wt% of polycyclic olefins; the norbornene derivatives include one or more of the compounds shown in formula (1) to (4). The cycloolefin monomer polymer is subjected to ring-opening polymerization and then hydrogenated to obtain a hydrogenated polymer. A specific norbornene derivative structural unit is introduced into the cycloolefin copolymer, and then the hydrogenated polymer is subjected to hydrogenation treatment, which can not only improve the ductility, but also make the transparency of the polymer more excellent, with a maximum elongation at break of 450%, a maximum transmittance of 94.1%, and a haze as low as 0.2%. It has good comprehensive performance. DETAILED DESCRIPTION

[0024] It should be understood that the expression "one or more of..." includes each of the items recited after the expression individually and in various different combinations of two or more of the recited items, unless otherwise understood from the context and usage. The expression "and / or" in combination with three or more recited items should be understood to have the same meaning, unless otherwise understood from the context.

[0025] The use of the terms "comprising", "having" or "containing", including their grammatical synonyms, should generally be understood as open and non-restrictive, for example not excluding other unrecited elements or steps, unless otherwise specifically stated or otherwise understood from the context.

[0026] It should be understood that the order of steps or the order in which certain actions are performed is not important as long as the application is still operable. In addition, two or more steps or actions can be performed simultaneously.

[0027] The use of any and all examples or exemplary language, such as "for example" or "including", herein is intended only to better illustrate the present application and does not limit the scope of the present application unless the claims are set forth. No language in this specification should be construed as indicating that any non-claimed element is essential to the practice of the present application.

[0028] In addition, the numerical ranges and parameters used to define the present application are approximate values, and the relevant values ​​in the specific embodiments have been presented as accurately as possible. However, any numerical value inherently inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise expressly stated, it should be understood that all ranges, quantities, values ​​and percentages used in this disclosure are modified by "about". Here, "about" generally means that the actual value is within plus or minus 10%, 5%, 1% or 0.5% of a specific value or range.

[0029] The present application is further described below in conjunction with the following embodiments. The protection scope of the present application is not limited by the following embodiments.

[0030] Example 1

[0031] This embodiment provides a norbornene derivative having a structure of formula (1), and a preparation method comprising:

[0032]

[0033]

[0034] Nitrogen was replaced in a 1L high temperature and high pressure reactor for 20 minutes, and 516g of styrene and 132g of dicyclopentadiene were vacuum sucked into the reactor. Stirring was started, and the reactor was raised to a reaction temperature of 220°C, reacted for 2 hours, cooled to room temperature, and the reaction liquid was vacuum sucked into a vacuum distillation device that was replaced with nitrogen for 30 minutes to purify the norbornene derivative with the structure of formula (1).

[0035] Example 2

[0036] This embodiment provides a norbornene derivative having a structure of formula (2), and a preparation method comprising:

[0037]

[0038] Nitrogen was replaced in a 1L high temperature and high pressure reactor for 20 minutes, and 585.5g of 2-methylstyrene and 132g of dicyclopentadiene were vacuum-absorbed into the reactor. Stirring was started, and the reactor was raised to a reaction temperature of 220°C, reacted for 2 hours, cooled to room temperature, and the reaction liquid was vacuum-absorbed into a vacuum distillation device that was replaced with nitrogen for 30 minutes to purify the norbornene derivative with the structure of formula (2).

[0039] Example 3

[0040] This embodiment provides a norbornene derivative having a structure of formula (3), and a preparation method comprising:

[0041]

[0042] Nitrogen was replaced in a 1L high temperature and high pressure reactor for 20 minutes, and 585.5g of 3-methylstyrene and 132g of dicyclopentadiene were vacuum-absorbed into the reactor. Stirring was started, and the reactor was raised to a reaction temperature of 220°C, reacted for 2 hours, cooled to room temperature, and the reaction liquid was vacuum-absorbed into a vacuum distillation device that was replaced with nitrogen for 30 minutes to purify the norbornene derivative with the structure of formula (3).

[0043] Example 4

[0044] This embodiment provides a norbornene derivative having a structure of formula (4), and a preparation method comprising:

[0045]

[0046]

[0047] Nitrogen was replaced in a 1L high temperature and high pressure reactor for 20 minutes, and 585.5g of 4-methylstyrene and 132g of dicyclopentadiene were vacuum-absorbed into the reactor. Stirring was started, and the reactor was raised to a reaction temperature of 220°C, reacted for 2 hours, cooled to room temperature, and the reaction liquid was vacuum-absorbed into a vacuum distillation device that was replaced with nitrogen for 30 minutes to purify the norbornene derivative with the structure of formula (4).

[0048] Example 5

[0049] A cycloolefin monomer composition comprises 5% of a norbornene derivative of formula (1) provided in Example 1, 7.5% of a norbornene derivative of formula (2) provided in Example 2, and 87.5% of dicyclopentadiene.

[0050] Using Grubbs2 as a ring-opening polymerization catalyst, the cycloolefin monomer composition was dissolved in toluene and subjected to ring-opening polymerization for 2 hours at a reaction temperature of 50°C and a stirring speed of 500 rpm. The reaction was stopped when the monomer conversion rate was ≥95%. After the polymerization was completed, a Pd-C catalyst with a polymer weight of 0.5% was used to hydrogenate in n-hexane at a reaction temperature of 60°C, a reaction pressure of 5 MPa, a stirring speed of 500 rpm, and a reaction time of 8 hours to obtain a hydrogenated polymer.

[0051] Example 6

[0052] A cycloolefin monomer composition comprises 5% of a norbornene derivative having a structure of formula (1) provided in Example 1, 7.5% of a norbornene derivative having a structure of formula (2) provided in Example 2, and 87.5% of tetracyclododecene.

[0053] Using Grubbs2 as a ring-opening polymerization catalyst, the cycloolefin monomer composition was dissolved in toluene and subjected to ring-opening polymerization for 2 hours at a reaction temperature of 50°C and a stirring speed of 500 rpm. The reaction was stopped when the monomer conversion rate was ≥95%. After the polymerization was completed, a Pd-C catalyst with a polymer weight of 0.5% was used to hydrogenate in n-hexane at a reaction temperature of 60°C, a reaction pressure of 5 MPa, a stirring speed of 500 rpm, and a reaction time of 8 hours to obtain a hydrogenated polymer.

[0054] Example 7

[0055] A cycloolefin monomer composition comprises 5% of a norbornene derivative having a structure of formula (1) provided in Example 1, 7.5% of a norbornene derivative having a structure of formula (2) provided in Example 2, and 87.5% of tricyclopentadiene.

[0056] Using Grubbs2 as a ring-opening polymerization catalyst, the cycloolefin monomer composition was dissolved in toluene and subjected to ring-opening polymerization for 2 hours at a reaction temperature of 50°C and a stirring speed of 500 rpm. The reaction was stopped when the monomer conversion rate was ≥95%. After the polymerization was completed, a Pd-C catalyst with a polymer weight of 0.5% was used to hydrogenate in n-hexane at a reaction temperature of 60°C, a reaction pressure of 5 MPa, a stirring speed of 500 rpm, and a reaction time of 8 hours to obtain a hydrogenated polymer.

[0057] Example 8

[0058] The cycloolefin monomer composition includes 0.001% of the norbornene derivative of the formula (3) provided in Example 3 and 99.999% of dicyclopentadiene.

[0059] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0060] Example 9

[0061] The cycloolefin monomer composition includes 10% of the norbornene derivative of the formula (1) provided in Example 1, 15% of the norbornene derivative of the formula (4) provided in Example 4, and 75% of dicyclopentadiene.

[0062] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0063] Example 10

[0064] The cycloolefin monomer composition includes 0.001% of the norbornene derivative of the formula (1) provided in Example 1 and 99.999% of dicyclopentadiene.

[0065] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0066] Embodiment 11

[0067] The cycloolefin monomer composition includes 5% of the norbornene derivative of formula (1) provided in Example 1, 7.5% of the norbornene derivative of formula (2) provided in Example 2, 47.5% of tetracyclododecene, and 40% of dicyclopentadiene.

[0068] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0069] Example 12

[0070] A cycloolefin monomer composition comprises 5% of a norbornene derivative of formula (1) provided in Example 1, 5% of a norbornene derivative of formula (2) provided in Example 2, 2.5% of a norbornene derivative of formula (3) provided in Example 3, and 87.5% of dicyclopentadiene.

[0071] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0072] Embodiment 13

[0073] A cycloolefin monomer composition comprises 2.5% of a norbornene derivative of formula (1) provided in Example 1, 5% of a norbornene derivative of formula (2) provided in Example 2, 2.5% of a norbornene derivative of formula (3) provided in Example 3, 2.5% of a norbornene derivative of formula (4) provided in Example 4, and 87.5% of dicyclopentadiene.

[0074] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0075] Embodiment 14

[0076] A cycloolefin monomer composition comprises 12.5% ​​of a norbornene derivative of the formula (1) provided in Example 1 and 87.5% of dicyclopentadiene.

[0077] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0078] Comparative Example 1

[0079] The cycloolefin monomer composition comprises 100% dicyclopentadiene.

[0080] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0081] Comparative Example 2

[0082] The cycloolefin monomer composition includes 15% of the norbornene derivative of the formula (1) provided in Example 1, 15% of the norbornene derivative of the formula (2) provided in Example 2, and 70% of dicyclopentadiene.

[0083] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0084] Comparative Example 3

[0085] The cycloolefin monomer composition includes 10% of the norbornene derivative of the formula (1) provided in Example 1, 20% of the norbornene derivative of the formula (2) provided in Example 2, and 70% of dicyclopentadiene.

[0086] The preparation method of the hydrogenated polymer is the same as that of Example 5.

[0087] The performance of the hydrogenated polymers prepared in Examples 5-11 and Comparative Examples 1-3 was tested in the following manner:

[0088] Light transmittance and haze (transparency): refer to GB / T 2410-2008 Determination of light transmittance and haze of transparent plastics A hazemeter method;

[0089] Elongation at break (ductility): The elongation at break test method is based on JIS K 7127 and is measured according to the following steps: The hydrogenated polymer is formed into a film having a thickness of about 100 μm by vacuum pressure hot pressing. The obtained molded body is punched out to make a test piece (type 5). Using a Tensilon universal testing machine (manufactured by ORIENTIC, product name "RTC-1125A"), a test is performed on the obtained test piece to be stretched to break at 23°C, a tensile speed of 50 mm / min, and a distance between chucks of 50 mm. The elongation at break is taken as the elongation at break (%).

[0090] The test results are shown in Table 1.

[0091] Table 1

[0092]

[0093]

[0094] The hydrogenated polymer prepared in this application has excellent ductility and transparency, with an elongation at break of up to 450%, a transmittance of up to 94.1%, and a haze of as low as 0.2%, which is significantly improved compared with the comparative examples. In comparative example 1, only dicyclopentadiene is added as a cycloolefin monomer, and the elongation at break is reduced to 170%, the transmittance is reduced to 91.9%, and the haze is increased to 0.6%; in comparative example 2, the amount of norbornene derivatives of formula (1) and formula (2) added in the preparation of the hydrogenated polymer exceeds the preferred range, and in comparative example 3, the amount of norbornene derivatives of formula (2) added exceeds the preferred range, which will also have a great impact on the performance.

[0095] The above is only a preferred specific implementation manner of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can make equivalent substitutions or changes within the technical scope disclosed in the present application according to the technical solution and application concept of the present application, which should be covered by the protection scope of the present application.

Claims

1. A cycloolefin monomer composition, characterized in that The composition comprises, by weight percentage, 0.001 wt % to 25 wt % of a norbornene derivative and 75 wt % to 99.999 wt % of a polycyclic olefin; The norbornene derivatives include one or more compounds represented by formula (1) to formula (4); 2. The cycloolefin monomer composition according to claim 1, characterized in that Including 0% to 10% of the compound represented by formula (1), 0% to 25% of the compound represented by formula (2), 0% to 25% of the compound represented by formula (3) and 0% to 25% of the compound represented by formula (4); The compounds represented by formula (1) to formula (4) are not 0 at the same time, and the total mass percentage of the compounds represented by formula (1) to formula (4) does not exceed 25%.

3. The cycloolefin monomer composition according to claim 1, characterized in that The polycyclic olefin structure is shown in formula (5): Wherein, R1 and R2 are hydrogen, phenyl with or without substituents, cycloalkyl or cycloalkenyl with or without substituents of C3 to C20, and R1 and R2 may form a ring; The polycyclic olefins include, but are not limited to, one or more of dicyclopentadiene, tricyclopentadiene, norbornene, methylnorbornene, ethylidene norbornene or tetracyclododecene.

4. A hydrogenated polymer, characterized in that Prepared from the cycloolefin monomer composition according to any one of claims 1 to 3.

5. A method for preparing a hydrogenated polymer, characterized in that: include: The cycloolefin monomer composition according to any one of claims 1 to 3 is subjected to a ring-opening polymerization reaction to obtain a ring-opening polymer; The ring-opening polymer is subjected to a hydrogenation reaction to obtain a hydrogenated polymer.

6. A film, characterized in that: Prepared by the hydrogenated polymer as claimed in claim 4.

7. An optical lens, characterized in that: Prepared by the hydrogenated polymer as claimed in claim 4.

8. Use of a hydrogenated polymer in the preparation of packaging materials.

9. The use according to claim 9, characterized in that: The packaging material includes pharmaceutical packaging material.

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