Cycloolefin copolymer, and method for producing and use thereof

Abstract

The application belongs to the technical field of high-performance polyolefins, and relates to a cyclic olefin copolymer as well as a preparation method and application thereof. The cyclic olefin copolymer is a binary random copolymer or a ternary random copolymer containing specific segments, and the molar content of each segment in the corresponding copolymer has a specific range. The preparation method comprises the following steps: under the protection of nitrogen or inert gas, a reaction monomer is dissolved in an organic solvent, a catalytic system is added to initiate a polymerization reaction, and then an anti-solvent is added to precipitate the product, so that the cyclic olefin copolymer is obtained; the catalytic system comprises a main catalyst, and the main catalyst is a half-molybdenum titanium metal catalyst or a double-molybdenum zirconium metal catalyst. The application is to prepare a blended film by blending the cyclic olefin copolymer with polypropylene. The application solves the problems of poor compatibility between ethylene-cyclic olefin copolymer and polypropylene and low heat distortion temperature of the blended film in the prior art.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high-performance polyolefins, and relates to a cyclic olefin copolymer and a preparation method and application thereof. BACKGROUND

[0002] Polypropylene has many advantages such as light weight, high strength, low moisture absorption, corrosion resistance, low cost, easy processing, etc. The film prepared by the biaxial stretching process of polypropylene is the core part of the film capacitor, and the performance of the polypropylene film significantly affects the dielectric strength, dielectric loss, insulation of the capacitor, etc., which is crucial to the safety and stability of new energy vehicles and high-end electronic devices. The current development of high-end electronic products puts forward higher requirements for the heat resistance and ultra-thinning of polypropylene films, but the heat distortion temperature of conventional polypropylene films is only 105-110℃.

[0003] Cyclic olefin copolymer (COC) is a kind of high-transparency, high-heat-resistant polymer material. In the existing modification technology, introducing cyclic olefin copolymer is an optimal way to improve the heat resistance of polypropylene film.

[0004] For example, patent application CN116368175A introduces 3-18wt% of cyclic olefin copolymer containing ethylene-norbornene, which increases the heat distortion temperature of polypropylene film to 145℃, and patent CN119529429B introduces 16-20wt% of cyclic olefin copolymer containing ethylene and unsaturated double bond on the ring and 0.2-0.3wt% of irradiation crosslinking agent, which increases the heat distortion temperature of polypropylene film to 152-160℃.

[0005] However, the cyclic olefin copolymers used in the above-mentioned existing technologies are all copolymers of ethylene and cyclic olefin monomers, and the ethylene segments in the molecular chain have large structural differences with the polypropylene matrix, and have poor compatibility, which is easy to cause phase separation during blending. Although the compatibility can be improved by adding a compatibilizer or a crosslinking agent, for high-end precision components such as polypropylene capacitor films, the residual and leakage of the compatibilizer and crosslinking agent in the ultra-thin film will seriously affect the performance of the device, and when chemical crosslinking is formed in the ultra-thin film, the arrangement of the molecular chain will inevitably change, forming wrinkles on the surface of the film, making it difficult to prepare a flat film.

[0006] Secondly, the above-mentioned existing technologies are still limited in improving the heat resistance of polypropylene film, and cannot meet the needs of high-end applications with higher heat distortion temperature.

[0007] In addition, the ethylene-cyclic olefin copolymer of the existing technology is theoretically a random copolymer, but there are inevitably small crystalline regions of ethylene segments in the preparation process. Once there is crystallization in the polymer, the film-forming property, transparency, and tear resistance of the formed blended film will be poor. SUMMARY

[0008] The application aims to solve the problems in the prior art and provide a cyclic olefin copolymer, a preparation method and application thereof.

[0009] To achieve the above-mentioned purpose, the application adopts the technical scheme as follows:

[0010] The cyclic olefin copolymer is a binary random copolymer containing 30-60 mol% of A segments and 40-70 mol% of X segments, wherein the X segment is a B segment, a C segment, a D segment, an E segment or a F segment.

[0011] Or a ternary random copolymer containing 30-60 mol% of A segments, 1-69 mol% of B segments and 1-69 mol% of Y segments, wherein the Y segment is a C segment, a D segment, an E segment or a F segment.

[0012] Or a ternary random copolymer containing 15-59 mol% of A segments, 40-70 mol% of X segments and 1-45 mol% of Z segments, wherein the Z segment is a G segment or a H segment.

[0013] The structural formulae of the A segment to the H segment are as follows:

[0014] 、 、 、 、 、 、 、 ;

[0015] In the formula, * represents the position of the segment connected to the main chain of the polymer, and a is an integer from 1 to 17.

[0016] As a preferred technical scheme:

[0017] The cyclic olefin copolymer has a number average molecular weight of 5-1000 kg / mol, a molecular weight distribution index of 1.1-6.0, an mr value of the propylene segment of 0.1-1.0 (therefore, adjacent propylene segments (i.e. A segments) are randomly distributed and are not easy to crystallize, and there is no small crystalline region of the propylene segment), a glass transition temperature (T g value) of 150-240℃, and a thermal decomposition temperature (T d value) of 380℃ or higher (therefore, the cyclic olefin copolymer has good heat resistance).

[0018] The application also provides a method for preparing the cyclic olefin copolymer according to any one of the above, wherein the reaction monomers are dissolved in an organic solvent (toluene, methylcyclohexane, cyclohexane, n-hexane, heptane, etc.) under the protection of nitrogen or inert gas, a catalytic system is added to initiate the polymerization reaction, and then an anti-solvent (hydrochloric acid ethanol solution) is added to precipitate the product, thereby obtaining the cyclic olefin copolymer.

[0019] The reaction monomers are a mixture of A monomers and X monomers, or the reaction monomers are a mixture of A monomers, B monomers and Y monomers, or the reaction monomers are a mixture of A monomers, X monomers and Z monomers.

[0020] The A monomers are reaction monomers corresponding to A segments, the X monomers are reaction monomers corresponding to X segments, the B monomers are reaction monomers corresponding to B segments, the Y monomers are reaction monomers corresponding to Y segments, and the Z monomers are reaction monomers corresponding to Z segments.

[0021] The catalytic system comprises a main catalyst, and the main catalyst is a half-metallocene titanium metal catalyst or a bis-metallocene zirconium metal catalyst. t MeSi[(Cp)Flu]TiMe2, CpTiCl2(NMe2)2, Me2Si(Cp)TiCl2(NMe2)2, t Bu2), t BuC5H4TiCl2(NMe2)2, [Me2Si(C5Me4)(NMe2)]TiCl2, t Bu2), [Me2Si(C5Me4)(NMe2)]TiCl2, t Bu)]TiCl2, and the bis-metallocene zirconium metal catalyst is i Pr[(Cp)Ind]ZrCl2, i Pr[(3-Me-Cp)Ind]ZrCl2, (CH2)2[(Ind)2]ZrCl2, Me2Si[(Ind)2]ZrCl2, i Pr[(Cp)Flu]ZrCl2.

[0022] The half-metallocene titanium metal catalyst or the bis-metallocene zirconium metal catalyst is used in the application to synthesize the cyclic olefin copolymer, and the activity is higher and the chain structure is more controllable, so that the cyclic olefin copolymer can match diversified commercial polypropylene raw materials. In the polymerization reaction, they can more accurately control the polymerization process of the reaction monomers, so that the segment distribution of the cyclic olefin copolymer is more in line with the expectation, thereby being able to match diversified commercial polypropylene raw materials. Compared with the uncontrollable segment distribution in the prior art, the application can effectively avoid the problem of insufficient matching with the polypropylene matrix caused by unreasonable segment distribution, thereby reducing the possibility of problems such as poor compatibility and crystallization defects.

[0023] As a preferred technical solution:

[0024] The method as described above, the molar ratio of the reaction monomer to the main catalyst is 2000:1-20000:1; the polymerization reaction time is 1-180 min, and the temperature is 0-150℃.

[0025] The method as described above, the catalytic system further comprises a cocatalyst; the cocatalyst is an aluminum-containing compound, and the molar ratio of the aluminum-containing compound to the main catalyst is 10:1-1000:1; or the cocatalyst is a boron-containing compound, and the molar ratio of the boron-containing compound to the main catalyst is 1.0:1-1.5:1.

[0026] The application further provides a blended film containing polypropylene and the cyclic olefin copolymer as described in any one of the above, and free of a crosslinking agent and a compatibilizer.

[0027] As a preferred technical solution:

[0028] The blended film as described above, the content of the polypropylene is 70-99wt%, the content of the cyclic olefin copolymer is 1-30wt%, and the total content of the polypropylene and the cyclic olefin copolymer is 100wt%.

[0029] The blended film as described above, the melting point of the polypropylene is 155-170℃, and the melt index is 2-10g / 10min.

[0030] The blended film as described above, the thickness of the blended film is 2-15μm, the heat distortion temperature is 150-168℃, and the heat shrinkage rate in the transverse direction and the longitudinal direction is not more than 3%.

[0031] The application further provides a method for preparing the blended film as described in any one of the above, which comprises the following steps: melting the polypropylene and the cyclic olefin copolymer, extruding and casting to obtain a base film, and then sequentially performing bidirectional stretching and heat setting treatment on the base film to obtain the blended film; and the process parameters include: the melting temperature is 230~270℃, the thickness of the base film is 25~135μm, the transverse stretching multiple is 2~8 times, the longitudinal stretching multiple is 2~8 times, and the heat setting treatment temperature is 160~180℃.

[0032] Principle of the application:

[0033] Compared with the ethylene-cyclic olefin copolymer in the prior art, the cyclic olefin copolymer in the application has better compatibility with the polypropylene, because the molecular chain structure of the polypropylene is as follows:

[0034] ;

[0035] The propylene segment of the cyclic olefin copolymer in the application has higher similarity to the molecular chain structure of the polypropylene than the ethylene segment in the ethylene-cyclic olefin copolymer in the prior art. Due to the good compatibility, it is not necessary to add a compatibilizer or a crosslinking agent when the blended film is prepared from the polypropylene and the cyclic olefin copolymer.

[0036] Compared with the ethylene-cyclic olefin copolymer of the prior art, the heat resistance of the propylene-based cyclic olefin copolymer of the present application is better, and the heat resistance of the blended film can be greatly improved, because the propylene segment of the cyclic olefin copolymer of the present application has one more methyl group than the ethylene segment of the prior art.

[0037] Although the cyclic olefin copolymer of the present application is also a random copolymer, the propylene segment (i.e. A segment) therein is more difficult to crystallize than the ethylene segment in the ethylene-cyclic olefin copolymer of the prior art, because polypropylene crystallization not only requires more propylene segments but also requires the propylene segments to be strictly isotactic / atactic arranged, while in the cyclic olefin copolymer of the present application, even if there are longer propylene continuous segments, these segments are randomly distributed, thus failing to meet the requirements of polypropylene crystallization, and thus are not easy to crystallize, ultimately having much less impact on the film-forming property, transparency and tear resistance of the blended film.

[0038] Advantages:

[0039] (1) The cyclic olefin copolymer of the present application contains propylene segments, has higher similarity with polypropylene molecular chain structure, and has good compatibility, so that no compatibilizer and crosslinking agent needs to be added when preparing the blended film, which can avoid the problems of device performance affected and film surface wrinkling caused by adding such substances, and is conducive to the preparation of smooth ultra-thin film with a thickness of 2-15 μm, solving the problems caused by the poor compatibility of ethylene-cyclic olefin copolymer and polypropylene in the prior art, which requires the addition of compatibilizer / crosslinking agent.

[0040] (2) The cyclic olefin copolymer of the present application has better heat resistance due to the structural characteristics of the propylene segment, and the film prepared by blending with polypropylene has a heat distortion temperature of 150-168℃, solving the problem that the heat distortion temperature of polypropylene film in the prior art is limited and cannot meet the needs of high-end applications.

[0041] (3) The cyclic olefin copolymer of the present application is a random copolymer, and the propylene segments are randomly distributed, which are more difficult to crystallize, and can avoid the problems of poor film-forming property, transparency and tear resistance of the blended film caused by the small crystalline region of the ethylene segment in the ethylene-cyclic olefin copolymer of the prior art, and optimize the comprehensive performance of the blended film.

[0042] (4) The cyclic olefin copolymer of the present application is synthesized by using a half-metallocene titanium metal catalyst or a double-metallocene zirconium metal catalyst, which has higher activity and stronger controllability of chain structure, can accurately control the distribution of segments, makes the cyclic olefin copolymer have good compatibility with the polypropylene matrix, avoids the problems of poor compatibility and crystallization defects caused by unreasonable segment distribution, supports the preparation of ultra-thin and high-heat-resistant film, and solves the problem of insufficient controllability of chain structure of the catalyst system in the prior art. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1NMR spectrum of carbon of the cyclic olefin copolymer prepared for Example 1. DETAILED DESCRIPTION

[0044] The application will be further described in conjunction with specific embodiments. It should be understood that these embodiments are only used for illustrating the application and not used for limiting the scope of the application. Furthermore, it should be understood that after reading the content taught by the application, those skilled in the art can make various modifications or changes to the application, and these equivalent forms also fall within the scope defined by the appended claims of the application.

[0045] The following are the test methods of the relevant performance indicators in each example and comparative example:

[0046] Melting point (T m ): The melting point of the polymer was determined by using a differential scanning calorimeter (DSC). 5 mg of sample was placed in an aluminum crucible and set to a temperature program of three stages of heating-cooling-heating (temperature range of 40-200℃, heating / cooling rate of 10℃ / min throughout): the sample was first kept at 40℃ for 2 min, then raised from 40℃ to 200℃ at a rate of 10℃ / min and kept at 200℃ for 2 min, then lowered from 200℃ to 40℃ at a rate of 10℃ / min and kept at 40℃ for 2 min, and finally raised from 40℃ to 200℃ at a rate of 10℃ / min; the endothermic peak on the second heating curve was analyzed using the analysis software provided with the instrument, and the melting point of the sample was obtained, with the unit of ℃;

[0047] Melt index (MFI): According to GB / T 3682.1-2018, the specific operation is as follows: 5 g of sample was loaded into the hopper of the melt index instrument, compacted and preheated at 230℃ for 30 min; after the piston was installed on the top of the hopper, 2.16 kg of load was added on top of the piston; after the sample was melted, the timing was started, and the sample strip extruded from the die was cut every 1 min, and the sample strip extruded within 10 min was collected; the collected sample strip was weighed on an analytical balance, and the total amount of sample strip extruded within 10 min was recorded, which was the melt index of the sample, with the unit of g / 10 min;

[0048] Number average molecular weight (M n) and molecular weight distribution (PDI): using high temperature gel permeation chromatograph (PLGPC-220) to determine, the specific operation is: take 10 mg sample into 10 mL 1,2,4-trichlorobenzene to obtain sample solution, heat to 150℃ on constant temperature oscillator and dissolve for 12 h; then use special filter gun to filter the sample solution into special sample bottle, place the sample bottle on the automatic sampler; set the test program, test at a flow rate of 1.0 mL / min, and the test results are analyzed by Cirrus software, i.e. the number average molecular weight and molecular weight distribution values are obtained; wherein the number average molecular weight unit is kg / mol, and the molecular weight distribution has no unit;

[0049] Molar content of chain segment, mr value of propylene chain segment: 50 mg of sample is dissolved in 0.6 mL of deuterated 1,1,2,2-tetrachloroethane solvent, and the sample is analyzed by nuclear magnetic resonance spectrometer (Bruker 600 MHz) to obtain the 13 C NMR test, according to the integral area of the characteristic peaks corresponding to different chain structure units, the molar content of the corresponding chain segment and the mr value of the propylene chain segment can be calculated;

[0050] Glass transition temperature (T g ): the glass transition temperature of the sample is determined by using a differential scanning calorimeter, 5 mg of sample is placed in an aluminum crucible, under a nitrogen atmosphere, the instrument temperature rising rate is set to 10℃ / min, the temperature range is 40-250℃, a three-stage program of rising-stable temperature-lowering temperature-rising temperature is set, the sample is kept at 40℃ for 2 min, then raised from 40℃ to 250℃ at a rate of 10℃ / min and kept at 250℃ for 2 min, then lowered from 250℃ to 40℃ at a rate of 10℃ / min and kept at 40℃ for 2 min, finally raised from 40℃ to 250℃ at a rate of 10℃ / min, the change position of the slope of the curve obtained from the second rising curve is analyzed by using the analysis software of the instrument, and the glass transition temperature of the polymer is obtained, which is ℃;

[0051] Thermal decomposition temperature (T d ): the thermal decomposition temperature of the sample is determined by using a thermal gravimetric analyzer (NETZSCH TG 209F1 Libra), 5 mg of polymer sample is placed in an alumina crucible, tested under a nitrogen atmosphere, the temperature rising rate is set to 10℃ / min, and the test temperature range is 35-800℃;

[0052] Heat distortion temperature: tested according to GB / T 1634.1-2019.

[0053] Example 1

[0054] A preparation method of a blended film, the specific steps are as follows:

[0055] (1) Preparation of materials;

[0056] Reaction monomers: composed of A monomers and X monomers, the A monomers are propylene, and the X monomers are norbornene (NB);

[0057] Organic solvent: toluene;

[0058] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is MeSi[(BuN)Flu]TiMe2, and the cocatalyst is triphenylmethyl tetrakis(pentafluorophenyl)borate; t

[0059] Anti-solvent: 5% hydrochloric acid ethanol solution by mass fraction;

[0060] Polypropylene: the melting point is 165℃, and the melt index is 10g / 10min;

[0061] (2) Preparation of a cyclic olefin copolymer;

[0062] Under the protection of nitrogen or inert gas, the reaction monomers are dissolved in the organic solvent, the catalytic system is added, and the polymerization reaction is carried out at 120℃ for 10min, and then the anti-solvent is added to precipitate the product, thereby obtaining the cyclic olefin copolymer; wherein, the molar volume ratio of the reaction monomers to the organic solvent is 1mol:0.5L, the molar ratio of the reaction monomers to the main catalyst is 2000:1, and the molar ratio of the cocatalyst to the main catalyst is 1:1;

[0063] The prepared cyclic olefin copolymer is a binary random copolymer containing 30mol% of A segments and 70mol% of X segments, and the X segments are B segments; the number average molecular weight of the cyclic olefin copolymer is 215kg / mol, the molecular weight distribution index is 1.2, the mr value of the propylene segment is 0.67, the glass transition temperature is 235℃, and the thermal decomposition temperature is 398℃; the nuclear magnetic resonance carbon spectrum of the cyclic olefin copolymer is as shown in Figure 1 ;

[0064] (3) Preparation of a blended film;

[0065] First, the polypropylene and the cyclic olefin copolymer are melted and extruded to obtain a base film, and then the base film is subjected to bidirectional stretching and heat setting treatment in sequence, thereby obtaining the blended film; wherein, the related process parameters are as follows: the melting temperature is 260℃, the thickness of the base film is 135μm, the bidirectional stretching multiple is 3 (i.e. the multiple of the transverse stretching and the multiple of the longitudinal stretching are both 3), and the heat setting treatment temperature is 160℃.

[0066] The content of the polypropylene in the finally prepared blended film is 70wt%, and the content of the cyclic olefin copolymer is 30wt%; the thickness of the blended film is 15μm, the heat distortion temperature is 160℃, the transverse heat shrinkage rate is 1.1%, and the longitudinal heat shrinkage rate is 1.9%.​

[0067] Comparative Example 1

[0068] A method for preparing a blend film, and the difference from Example 1 is that the A monomer is replaced by an equal molar amount of ethylene monomer.

[0069] The heat distortion temperature of the finally prepared blend film is 148°C, the transverse heat shrinkage rate is 3.1%, and the longitudinal heat shrinkage rate is 3.6%.

[0070] Compared with Comparative Example 1 and Example 1, the heat distortion temperature of the blend film is significantly reduced, and the transverse and longitudinal heat shrinkage rates of the film increase, because after replacing the propylene monomer with an equal molar amount of ethylene monomer, the glass transition temperature of the prepared cyclic olefin copolymer is reduced, and the compatibility of the prepared cyclic olefin copolymer with the polypropylene matrix is poor, there are defects such as phase separation during the film stretching process, resulting in a reduced heat distortion temperature and an increased heat shrinkage rate.

[0071] Comparative Example 2

[0072] A method for preparing a blend film, and the difference from Example 1 is that the A monomer is replaced by an equal molar amount of 1-hexene monomer.

[0073] The heat distortion temperature of the finally prepared blend film is 145°C, the transverse heat shrinkage rate is 3.5%, and the longitudinal heat shrinkage rate is 4.0%.

[0074] Compared with Comparative Example 2 and Example 1, the heat distortion temperature of the blend film is significantly reduced, and the transverse and longitudinal heat shrinkage rates of the film increase, because after replacing the propylene monomer with an equal molar amount of 1-hexene monomer, the prepared cyclic olefin copolymer has increased molecular chain movement ability due to the presence of longer branches, its glass transition temperature is reduced, and the compatibility of the prepared cyclic olefin copolymer with the polypropylene matrix is poor, there are defects such as phase separation during the film stretching process, resulting in a reduced heat distortion temperature and an increased heat shrinkage rate.

[0075] Comparative Example 3

[0076] A method for preparing a blend film, and the difference from Example 1 is that the feeding ratio of the A monomer and the X monomer is adjusted, and the cyclic olefin copolymer prepared in step (2) is a binary random copolymer containing 25 mol% of A segments and 75 mol% of X segments.

[0077] The heat distortion temperature of the finally prepared blend film is 149°C, the transverse heat shrinkage rate is 3.0%, and the longitudinal heat shrinkage rate is 3.2%.

[0078] Compared with Example 1, the heat distortion temperature of the blended film of Comparative Example 3 is obviously decreased, and the heat shrinkage of the film in the transverse and longitudinal directions is increased, because the prepared cyclic olefin copolymer has a decreased proportion of propylene segments, a poor compatibility with the polypropylene matrix, and defects such as phase separation during the film stretching, which results in a decreased heat distortion temperature and an increased heat shrinkage.

[0079] Example 2

[0080] A method for preparing a blended film, and the specific steps are as follows:

[0081] (1) Preparation of materials;

[0082] Reaction monomers: composed of A monomers and X monomers, the A monomers are propylene, and the X monomers are tetracyclododecene (TCD);

[0083] Organic solvent: methylcyclohexane;

[0084] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is CpTiCl2(N= t Bu2), and the cocatalyst is methylaluminoxane (CAS No. 120144-90-3);

[0085] Anti-solvent: a 5% hydrochloric acid ethanol solution;

[0086] Polypropylene: a melting point of 163℃ and a melt index of 5g / 10min;

[0087] (2) Preparation of a cyclic olefin copolymer;

[0088] Under the protection of nitrogen or inert gas, the reaction monomers are dissolved in the organic solvent, the catalytic system is added, and the polymerization reaction is carried out at 0℃ for 180min, and then the anti-solvent is added to precipitate the product, to obtain the cyclic olefin copolymer; wherein, the molar volume ratio of the reaction monomers to the organic solvent is 1mol:1L, the molar ratio of the reaction monomers to the main catalyst is 5000:1, and the molar ratio of the cocatalyst to the main catalyst is 10:1;

[0089] The prepared cyclic olefin copolymer is a binary random copolymer containing 32mol% of A segments and 68mol% of X segments, and the X segments are C segments; the number average molecular weight of the cyclic olefin copolymer is 1000kg / mol, the molecular weight distribution index is 1.1, the mr value of the propylene segments is 0.1, the glass transition temperature is 218℃, and the thermal decomposition temperature is 392℃;

[0090] (3) Preparation of a blended film;

[0091] The polypropylene and the cyclic olefin copolymer are first melted and then extrusion cast to obtain a base film, and then the base film is subjected to biaxial stretching and heat setting treatment in sequence to obtain the blended film; wherein the related process parameters are: melting temperature 250℃, base film thickness 48μm, biaxial stretching multiple 2 times (i.e. the multiple of the transverse stretching and the multiple of the longitudinal stretching are both 2 times), heat setting treatment temperature 170℃.

[0092] The content of the polypropylene in the finally prepared blended film is 75wt%, and the content of the cyclic olefin copolymer is 25wt%; the thickness of the blended film is 12μm, the heat distortion temperature is 156℃, the transverse heat shrinkage rate is 3%, and the longitudinal heat shrinkage rate is 3%.

[0093] Example 3

[0094] A preparation method of a blended film, the specific steps are as follows:

[0095] (1) Preparation of materials;

[0096] Reaction monomers: composed of A monomers and X monomers, the A monomers are propylene, and the X monomers are 1,4,5,8,9,10-trimethylene dodecahydroanthracene;

[0097] Organic solvent: cyclohexane;

[0098] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is t BuC5H4TiCl2(N= t Bu2), and the cocatalyst is triphenylmethyl tetrakis(pentafluorophenyl) borate;

[0099] Anti-solvent: 5% hydrochloric acid ethanol solution by mass fraction;

[0100] Polypropylene: melting point 155℃, melt index 9g / 10min;

[0101] (2) Preparation of a cyclic olefin copolymer;

[0102] Under the protection of nitrogen or inert gas, the reaction monomers are dissolved in the organic solvent, the catalytic system is added, and the polymerization reaction is carried out at 40℃ for 60min, and then the anti-solvent is added to precipitate the product, to obtain the cyclic olefin copolymer; wherein the molar volume ratio of the reaction monomers to the organic solvent is 1mol:2L, the molar ratio of the reaction monomers to the main catalyst is 8000:1, and the molar ratio of the cocatalyst to the main catalyst is 1.2:1;

[0103] The prepared cyclic olefin copolymer is a binary random copolymer containing 36 mol% of A segments and 64 mol% of X segments, the X segment is D segment; the number average molecular weight of the cyclic olefin copolymer is 406 kg / mol, the molecular weight distribution index is 1.5, the mr value of the propylene segment is 0.44, the glass transition temperature is 204°C, and the thermal decomposition temperature is 382°C;

[0104] (3) preparing a blended film;

[0105] First, melt the polypropylene and the cyclic olefin copolymer, extrude and cast to obtain a base film, and then sequentially perform bidirectional stretching and heat setting treatment on the base film to obtain the blended film; wherein the related process parameters are: a melting temperature of 240°C, a base film thickness of 62.5 μm, a bidirectional stretching multiple of 2.5 times (i.e., the horizontal and vertical stretching multiples are both 2.5 times), and a heat setting treatment temperature of 180°C.

[0106] The final blended film has a polypropylene content of 78 wt% and a cyclic olefin copolymer content of 22 wt%; the thickness of the blended film is 10 μm, the heat distortion temperature is 150°C, the horizontal heat shrinkage rate is 1.4%, and the vertical heat shrinkage rate is 1.5%.

[0107] Example 4

[0108] A method for preparing a blended film, the specific steps are as follows:

[0109] (1) preparation of materials;

[0110] Reaction monomers: composed of A monomers and X monomers, the A monomers are propylene, and the X monomers are dicyclopentadiene (DCPD);

[0111] Organic solvent: n-hexane;

[0112] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is [Me2Si(C5Me4)(N t Bu)]TiCl2, and the cocatalyst is modified methylaluminoxane (manufacturer: Japan TOSOH Corporation, brand: MMAO-3A);

[0113] Anti-solvent: 5% hydrochloric acid in ethanol;

[0114] Polypropylene: melting point of 168°C, melt index of 4 g / 10 min;

[0115] (2) preparing a cyclic olefin copolymer;

[0116] The reaction monomer is dissolved in an organic solvent under the protection of nitrogen or inert gas, a catalytic system is added, and the polymerization reaction is carried out at 60℃ for 120 min, and then a counter solvent is added to precipitate the product, so that the cyclic olefin copolymer is obtained; wherein, the molar volume ratio of the reaction monomer to the organic solvent is 1 mol:3 L, the molar ratio of the reaction monomer to the main catalyst is 10000:1, and the molar ratio of the cocatalyst to the main catalyst is 1000:1;

[0117] The prepared cyclic olefin copolymer is a binary random copolymer containing 41 mol% of A segments and 59 mol% of X segments, and the X segment is an E segment; the number average molecular weight of the cyclic olefin copolymer is 680 kg / mol, the molecular weight distribution index is 3.8, the mr value of the propylene segment is 0.51, the glass transition temperature is 178℃, and the thermal decomposition temperature is 389℃;

[0118] (3) preparing a blended film;

[0119] First, the polypropylene and the cyclic olefin copolymer are melted and extruded to obtain a base film, and then the base film is subjected to bidirectional stretching and heat setting treatment in sequence, so that the blended film is obtained; wherein, the related process parameters are as follows: the melting temperature is 245℃, the thickness of the base film is 81 μm, the bidirectional stretching multiple is 3 times (i.e. the multiple of the transverse stretching and the multiple of the longitudinal stretching are both 3 times), and the heat setting treatment temperature is 160℃.

[0120] The content of the polypropylene in the finally prepared blended film is 82 wt%, and the content of the cyclic olefin copolymer is 18 wt%; the thickness of the blended film is 9 μm, the heat distortion temperature is 162℃, the transverse heat shrinkage rate is 0.8%, and the longitudinal heat shrinkage rate is 1.1%.

[0121] Example 5

[0122] A preparation method of a blended film, and the specific steps are as follows:

[0123] (1) preparation of materials;

[0124] Reaction monomer: composed of A monomer and X monomer, the A monomer is propylene, and the X monomer is pentacyclo[6.5.1.1 3 ,6.0 2 ,7.0 9 ,1 3 ]-4-pentadecene;

[0125] Organic solvent: heptane;

[0126] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is i Pr[(Cp)Ind]ZrCl2, and the cocatalyst is N,N-dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate;

[0127] Anti-solvent: 5% hydrochloric acid in ethanol by mass fraction;

[0128] Polypropylene: melting point 170℃, melt index 8g / 10min;

[0129] (2) Preparation of cyclic olefin copolymer;

[0130] Dissolve the reaction monomers in the organic solvent under the protection of nitrogen or inert gas, add the catalytic system, and polymerize at 80℃ for 150min, then add the anti-solvent to precipitate the product, thereby obtaining the cyclic olefin copolymer; wherein the molar volume ratio of the reaction monomers to the organic solvent is 1mol:4L, the molar ratio of the reaction monomers to the main catalyst is 12000:1, and the molar ratio of the co-catalyst to the main catalyst is 1.5:1;

[0131] The prepared cyclic olefin copolymer is a binary random copolymer containing 60mol% A segments and 40mol% X segments, and the X segment is F segment; the number average molecular weight of the cyclic olefin copolymer is 820kg / mol, the molecular weight distribution index is 4.2, the mr value of the propylene segment is 0.36, the glass transition temperature is 150℃, and the thermal decomposition temperature is 380℃;

[0132] (3) Preparation of blended film;

[0133] First, melt the polypropylene and the cyclic olefin copolymer, extrude and cast to obtain a base film, and then sequentially perform bidirectional stretching and heat setting treatment on the base film, thereby obtaining the blended film; wherein the relevant process parameters are: melting temperature 235℃, base film thickness 54μm, bidirectional stretching multiple 3 (i.e. the horizontal and vertical stretching multiples are both 3), and heat setting treatment temperature 170℃.

[0134] The final blended film contains 86wt% polypropylene and 14wt% cyclic olefin copolymer; the thickness of the blended film is 6μm, the heat distortion temperature is 162℃, the horizontal heat shrinkage rate is 1.9%, and the vertical heat shrinkage rate is 2%.

[0135] Example 6

[0136] A method for preparing a blended film, the specific steps are as follows:

[0137] (1) Preparation of materials;

[0138] Reaction monomers: composed of A monomers, B monomers and Y monomers, A monomers are propylene, B monomers are norbornene (NB), and Y monomers are tetracyclododecene (TCD);

[0139] Organic solvent: toluene;

[0140] Catalytic system: composed of a main catalyst and a co-catalyst, the main catalyst isi Pr[(Cp)Ind]ZrCl2, triethylaluminum as the cocatalyst;

[0141] Anti-solvent: 5% hydrochloric acid in ethanol;

[0142] Polypropylene: melting point 170℃, melt index 3g / 10min;

[0143] (2) Preparation of cyclic olefin copolymer;

[0144] The reaction monomer is dissolved in an organic solvent under the protection of nitrogen or inert gas, the catalytic system is added, and the polymerization reaction is carried out at 140℃ for 1min, and then the anti-solvent is added to precipitate the product, thereby obtaining the cyclic olefin copolymer; wherein the molar volume ratio of the reaction monomer to the organic solvent is 1mol:6L, the molar ratio of the reaction monomer to the main catalyst is 2000:1, and the molar ratio of the cocatalyst to the main catalyst is 200:1;

[0145] The prepared cyclic olefin copolymer is a ternary random copolymer containing 30mol% of A segment, 1mol% of B segment and 69mol% of Y segment, and the Y segment is C segment; the number average molecular weight of the cyclic olefin copolymer is 5kg / mol, the molecular weight distribution index is 2.6, the mr value of the propylene segment is 0.72, the glass transition temperature is 238℃, and the thermal decomposition temperature is 399℃;

[0146] (3) Preparation of blended film;

[0147] First, the polypropylene and the cyclic olefin copolymer are melted and extrusion cast to obtain a base film, and then the base film is subjected to bidirectional stretching and heat setting treatment in sequence, thereby obtaining the blended film; wherein the related process parameters are as follows: melting temperature 265℃, base film thickness 25μm, bidirectional stretching multiple 2.5 times (i.e. the horizontal and vertical stretching multiples are both 2.5 times), and heat setting treatment temperature 180℃.

[0148] The final blended film contains 99wt% of polypropylene and 1wt% of cyclic olefin copolymer; the thickness of the blended film is 4μm, the heat distortion temperature is 168℃, the horizontal heat shrinkage rate is 1.2%, and the vertical heat shrinkage rate is 1.5%.

[0149] Example 7

[0150] A method for preparing a blended film, the specific steps are as follows:

[0151] (1) Preparation of materials;

[0152] Reaction monomer: composed of A monomer, B monomer and Y monomer, the A monomer is propylene, the B monomer is norbornene (NB), and the Y monomer is 1,4,5,8,9,10-trimethylenedodecahydroanthracene;

[0153] Organic solvent: methylcyclohexane;

[0154] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is (CH2)2[(Ind)2]ZrCl2, and the cocatalyst is N,N-dimethylphenylammonium tetrakis(pentafluorophenyl)borate;

[0155] Anti-solvent: 5% hydrochloric acid ethanol solution by mass fraction;

[0156] Polypropylene: melting point of 166℃, melt index of 7g / 10min;

[0157] (2) Preparation of cyclic olefin copolymer;

[0158] Dissolve the reaction monomer in the organic solvent under the protection of nitrogen or inert gas, add the catalytic system, and polymerize at 100℃ for 30min, then add the anti-solvent to precipitate the product, thereby obtaining the cyclic olefin copolymer; wherein, the molar volume ratio of the reaction monomer to the organic solvent is 1mol:8L, the molar ratio of the reaction monomer to the main catalyst is 15000:1, and the molar ratio of the cocatalyst to the main catalyst is 1:1;

[0159] The prepared cyclic olefin copolymer is a ternary random copolymer containing 52mol% of A segment, 14mol% of B segment and 34mol% of Y segment, and the Y segment is D segment; the number average molecular weight of the cyclic olefin copolymer is 82kg / mol, the molecular weight distribution index is 5.0, the mr value of the propylene segment is 0.85, the glass transition temperature is 182℃, and the thermal decomposition temperature is 396℃;

[0160] (3) Preparation of blended film;

[0161] First, melt the polypropylene and the cyclic olefin copolymer, extrude and cast to obtain a base film, and then sequentially perform bidirectional stretching and heat setting treatment on the base film, thereby obtaining the blended film; wherein, the related process parameters are: melting temperature 255℃, base film thickness 128μm, bidirectional stretching multiple 8 times (i.e. the horizontal and vertical stretching multiples are both 8 times), and heat setting treatment temperature 160℃.

[0162] The final prepared blended film contains 90wt% of polypropylene and 10wt% of cyclic olefin copolymer; the thickness of the blended film is 2μm, the heat distortion temperature is 164℃, the horizontal heat shrinkage rate is 2%, and the vertical heat shrinkage rate is 2.8%.

[0163] Example 8

[0164] A preparation method of a blended film, the specific steps are as follows:

[0165] (1) Preparation of materials;

[0166] Reaction monomer: composed of A monomer, B monomer and Y monomer, the A monomer is propylene, the B monomer is norbornene (NB), and the Y monomer is dicyclopentadiene (DCPD);

[0167] Organic solvent: toluene;

[0168] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is Me2Si[(Ind)2]ZrCl2, and the cocatalyst is methylaluminoxane (CAS No. 120144-90-3);

[0169] Anti-solvent: 5% hydrochloric acid ethanol solution by mass fraction;

[0170] Polypropylene: the melting point is 169℃, and the melt index is 2g / 10min;

[0171] (2) Preparation of a cyclic olefin copolymer;

[0172] The reaction monomer was dissolved in the organic solvent under the protection of nitrogen or inert gas, the catalytic system was added, and the polymerization reaction was carried out at 150℃ for 5min, and then the anti-solvent was added to precipitate the product, thereby obtaining the cyclic olefin copolymer; wherein, the molar volume ratio of the reaction monomer to the organic solvent was 1mol:5L, the molar ratio of the reaction monomer to the main catalyst was 18000:1, and the molar ratio of the cocatalyst to the main catalyst was 500:1;

[0173] The prepared cyclic olefin copolymer was a ternary random copolymer containing 57mol% of A segments, 22mol% of B segments and 21mol% of Y segments, and the Y segment was an E segment; the number average molecular weight of the cyclic olefin copolymer was 530kg / mol, the molecular weight distribution index was 6.0, the mr value of the propylene segment was 1, the glass transition temperature was 171℃, and the thermal decomposition temperature was 397℃;

[0174] (3) Preparation of a blended film;

[0175] First, the polypropylene and the cyclic olefin copolymer were melted and extrusion cast to obtain a base film, and then the base film was subjected to bidirectional stretching and heat setting treatment in sequence, thereby obtaining the blended film; wherein, the related process parameters were as follows: the melting temperature was 260℃, the base film thickness was 121.5μm, the bidirectional stretching multiple was 4.5 times (i.e. the horizontal and vertical stretching multiples were both 4.5 times), and the heat setting treatment temperature was 170℃.

[0176] The content of the polypropylene in the finally prepared blended film was 92wt%, and the content of the cyclic olefin copolymer was 8wt%; the thickness of the blended film was 6μm, the heat distortion temperature was 163℃, the horizontal heat shrinkage rate was 2.2%, and the vertical heat shrinkage rate was 2.4%.

[0177] Example 9

[0178] A preparation method of a blended film, the specific steps are as follows:

[0179] (1) Preparation of materials;

[0180] Reaction monomers: composed of A monomers, B monomers and Y monomers, A monomers are propylene, B monomers are norbornene (NB), and Y monomers are dicyclopentadiene (DCPD);

[0181] Organic solvent: methylcyclohexane;

[0182] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is i Pr[(Cp)Flu]ZrCl2, and the cocatalyst is N,N-dihexadecylphenylammonium tetrakis(pentafluorophenyl)borate;

[0183] Anti-solvent: 5% hydrochloric acid ethanol solution;

[0184] Polypropylene: melting point 158℃, melt index 6g / 10min;

[0185] (2) Preparation of a cyclic olefin copolymer;

[0186] Under the protection of nitrogen or inert gas, the reaction monomers are dissolved in the organic solvent, the catalytic system is added, and the polymerization reaction is carried out at 20℃ for 180min, then the anti-solvent is added to precipitate the product, and the cyclic olefin copolymer is obtained; wherein the molar volume ratio of the reaction monomers to the organic solvent is 1mol:10L, the molar ratio of the reaction monomers to the main catalyst is 20000:1, and the molar ratio of the cocatalyst to the main catalyst is 1.3:1;

[0187] The prepared cyclic olefin copolymer is a ternary random copolymer containing 30mol% A segments, 69mol% B segments and 1mol% Y segments, and the Y segment is an F segment; the number average molecular weight of the cyclic olefin copolymer is 741kg / mol, the molecular weight distribution index is 2.2, the mr value of the propylene segment is 0.93, the glass transition temperature is 240℃, and the thermal decomposition temperature is 399℃;

[0188] (3) Preparation of a blended film;

[0189] First, the polypropylene and the cyclic olefin copolymer are melted and extruded to obtain a base film, and then the base film is subjected to bidirectional stretching and heat setting treatment in sequence, and the blended film is obtained; wherein the relevant process parameters are: melting temperature 270℃, base film thickness 98μm, bidirectional stretching multiple 7 times (i.e. the transverse stretching multiple and the longitudinal stretching multiple are both 7 times), and heat setting treatment temperature 180℃.

[0190] The content of the polypropylene in the finally prepared blending film is 95wt%, and the content of the cyclic olefin copolymer is 5wt%; the thickness of the blending film is 2μm, the heat distortion temperature is 153℃, the transverse heat shrinkage rate is 2.4%, and the longitudinal heat shrinkage rate is 2.6%.

[0191] Example 10

[0192] A method for preparing a blending film, and the specific steps are as follows:

[0193] (1) Preparation of materials;

[0194] Reaction monomers: composed of A monomers, X monomers and Z monomers, the A monomers are propylene, the X monomers are norbornene (NB), and the Z monomers are ethylene;

[0195] Organic solvent: toluene;

[0196] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is MeSi[(BuN)Flu]TiMe2, and the cocatalyst is tris(pentafluorophenyl)boron; t

[0197] Anti-solvent: 5% hydrochloric acid ethanol solution by mass fraction;

[0198] Polypropylene: the melting point is 163℃, and the melt index is 5g / 10min;

[0199] (2) Preparation of a cyclic olefin copolymer;

[0200] Under the protection of nitrogen or inert gas, the reaction monomers are dissolved in the organic solvent, the catalytic system is added, and the polymerization reaction is carried out at 75℃ for 40min, and then the anti-solvent is added to precipitate the product, thereby obtaining the cyclic olefin copolymer; wherein, the molar volume ratio of the reaction monomers to the organic solvent is 1mol:2L, the molar ratio of the reaction monomers to the main catalyst is 5000:1, and the molar ratio of the cocatalyst to the main catalyst is 1:1;

[0201] The prepared cyclic olefin copolymer is a ternary random copolymer containing 15mol% of A segments, 40mol% of X segments and 45mol% of Z segments, the X segments are B segments, and the Z segments are G segments; the number average molecular weight of the cyclic olefin copolymer is 389kg / mol, the molecular weight distribution index is 1.4, the mr value of the propylene segment is 0.33, the glass transition temperature is 180℃, and the thermal decomposition temperature is 385℃;

[0202] (3) Preparation of a blending film;

[0203] ​The polypropylene and the cyclic olefin copolymer are first melted and then extruded to obtain a base film, and then the base film is subjected to bidirectional stretching and heat setting, to obtain the blended film; wherein the related process parameters are: melting temperature 230℃, base film thickness 90μm, bidirectional stretching multiple 3 (i.e. the multiple of the transverse stretching and the multiple of the longitudinal stretching are both 3), heat setting temperature 160℃.

[0204] The content of the polypropylene in the finally obtained blended film is 73wt%, and the content of the cyclic olefin copolymer is 27wt%; the thickness of the blended film is 10μm, the heat distortion temperature is 161℃, the transverse heat shrinkage rate is 1.6%, and the longitudinal heat shrinkage rate is 1.8%.

[0205] Example 11

[0206] A method for preparing a blended film, the specific steps are as follows:

[0207] (1) Preparation of materials;

[0208] Reaction monomers: composed of A monomers, X monomers and Z monomers, the A monomers are propylene, the X monomers are tetracyclododecene (TCD), and the Z monomers are 1-hexene;

[0209] Organic solvent: methylcyclohexane;

[0210] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is CpTiCl2(N= t Bu2), and the cocatalyst is triisobutylaluminum;

[0211] Anti-solvent: 5% hydrochloric acid ethanol solution;

[0212] Polypropylene: melting point 165℃, melt index 9g / 10min;

[0213] (2) Preparation of a cyclic olefin copolymer;

[0214] Under the protection of nitrogen or inert gas, the reaction monomers are dissolved in the organic solvent, the catalytic system is added, and the polymerization reaction is carried out at 85℃ for 45min, and then the anti-solvent is added to precipitate the product, to obtain the cyclic olefin copolymer; wherein the molar volume ratio is 1mol:3L, the molar ratio of the reaction monomers to the main catalyst is 8000:1, and the molar ratio of the cocatalyst to the main catalyst is 300:1;

[0215] The prepared cyclic olefin copolymer is a ternary random copolymer containing 20 mol% of A segment, 70 mol% of X segment and 10 mol% of Z segment, the X segment is C segment, and the Z segment is H segment (a=3); the number average molecular weight of the cyclic olefin copolymer is 528 kg / mol, the molecular weight distribution index is 1.5, the mr value of the propylene segment is 0.54, the glass transition temperature is 162°C, and the thermal decomposition temperature is 397°C;

[0216] (3) preparing a blended film;

[0217] First, the polypropylene and the cyclic olefin copolymer are melted and extrusion cast to obtain a base film, and then the base film is subjected to bidirectional stretching and heat setting treatment in sequence to obtain the blended film; wherein the related process parameters are as follows: the melting temperature is 245°C, the thickness of the base film is 108 μm, the bidirectional stretching multiple is 6 times (i.e. the multiple of the transverse stretching and the multiple of the longitudinal stretching are both 6 times), and the heat setting treatment temperature is 170°C.

[0218] The content of the polypropylene in the finally prepared blended film is 77 wt%, and the content of the cyclic olefin copolymer is 23 wt%; the thickness of the blended film is 3 μm, the heat distortion temperature is 163°C, the transverse heat shrinkage rate is 2.1%, and the longitudinal heat shrinkage rate is 2.1%.

[0219] Example 12

[0220] A method for preparing a blended film, the specific steps are as follows:

[0221] (1) preparation of materials;

[0222] Reaction monomers: composed of A monomers, X monomers and Z monomers, the A monomers are propylene, the X monomers are 1,4,5,8,9,10-trimethylene dodecahydroanthracene, and the Z monomers are 1-octene;

[0223] Organic solvent: toluene;

[0224] Catalytic system: composed of a main catalyst and a cocatalyst, the main catalyst is CpTiCl2(N= t Bu2), and the cocatalyst is modified methylaluminoxane (manufacturer: Japan TOSOH Corporation, brand: MMAO-3A);

[0225] Anti-solvent: 5% hydrochloric acid ethanol solution;

[0226] Polypropylene: the melting point is 170°C, and the melt index is 3 g / 10 min;

[0227] (2) preparing a cyclic olefin copolymer;

[0228] Under nitrogen or inert gas protection, the reactive monomer is dissolved in an organic solvent, added to the catalytic system, and polymerized at 95°C for 60 min. Then, an antisolvent is added to precipitate the product, thus obtaining the cyclic olefin copolymer. The molar volume ratio is 1 mol: 4 L, the molar ratio of reactive monomer to main catalyst is 10000: 1, and the molar ratio of co-catalyst to main catalyst is 600: 1.

[0229] The obtained cyclic olefin copolymer is a ternary random copolymer containing 47 mol% A segment, 50 mol% X segment and 3 mol% Z segment, where X segment is D segment and Z segment is H segment (a=5); the number average molecular weight of the cyclic olefin copolymer is 920 kg / mol, the molecular weight distribution index is 1.8, the mr value of the propylene segment is 0.61, the glass transition temperature is 173℃, and the thermal decomposition temperature is 394℃.

[0230] (3) Preparation of blended thin films;

[0231] First, the polypropylene and cyclic olefin copolymer is melted and then extruded and cast to obtain a base film. The base film is then subjected to biaxial stretching and heat setting treatment to obtain a blended film. The relevant process parameters are: melt temperature 255℃, base film thickness 121μm, biaxial stretching ratio 5.5 times (i.e., both the transverse stretching ratio and the longitudinal stretching ratio are 5.5 times), and heat setting treatment temperature 180℃.

[0232] The final blended film contained 85 wt% polypropylene and 15 wt% cyclic olefin copolymer; the thickness of the blended film was 4 μm, the heat distortion temperature was 166 °C, the transverse heat shrinkage rate was 1.3%, and the longitudinal heat shrinkage rate was 1.7%.

[0233] Example 13

[0234] A method for preparing a blended thin film, comprising the following specific steps:

[0235] (1) Preparation of materials;

[0236] Reaction monomers: composed of monomer A, monomer X, and monomer Z, where monomer A is propylene and monomer X is a pentacyclic ring [6.5.1.1]. 3 6.0 2 7.0 9 ,1 3 ]-4-Pentadecene, Z monomer is ethylene;

[0237] Organic solvent: methylcyclohexane;

[0238] Catalytic system: Composed of a main catalyst and a co-catalyst, the main catalyst being MeSi[( t BuN)Flu]TiMe2, with triphenylmethyltetra(pentafluorophenyl)borate as the co-catalyst;

[0239] Anti-solvent: 5% hydrochloric acid in ethanol;

[0240] Polypropylene: melting point 170℃, melt index 3g / 10min;

[0241] (2) Preparation of cyclic olefin copolymer;

[0242] The reaction monomer was dissolved in an organic solvent under the protection of nitrogen or inert gas, a catalytic system was added, and the polymerization reaction was carried out at 100℃ for 75min, and then an anti-solvent was added to precipitate the product, thereby obtaining the cyclic olefin copolymer; wherein, the molar volume ratio was 1mol:6L, the molar ratio of the reaction monomer to the main catalyst was 12000:1, and the molar ratio of the co-catalyst to the main catalyst was 1.2:1;

[0243] The prepared cyclic olefin copolymer was a ternary random copolymer containing 59mol% of A segment, 40mol% of X segment and 1mol% of Z segment, the X segment was F segment, and the Z segment was H segment (a=9); the number average molecular weight of the cyclic olefin copolymer was 105kg / mol, the molecular weight distribution index was 2.1, the mr value of the propylene segment was 0.4, the glass transition temperature was 177℃, and the thermal decomposition temperature was 388℃;

[0244] (3) Preparation of blended film;

[0245] First, the polypropylene and the cyclic olefin copolymer were melted and extrusion cast to obtain a base film, and then the base film was subjected to bidirectional stretching and heat setting treatment in sequence, thereby obtaining the blended film; wherein, the related process parameters were as follows: melting temperature 260℃, base film thickness 112.5μm, bidirectional stretching multiple 7.5 times (i.e. the horizontal and vertical stretching multiples were both 7.5 times), and heat setting treatment temperature 160℃.

[0246] The final blended film contained 88wt% of polypropylene and 12wt% of cyclic olefin copolymer; the thickness of the blended film was 2μm, the heat distortion temperature was 167℃, the horizontal heat shrinkage rate was 1.7%, and the vertical heat shrinkage rate was 1.9%.

Claims

1. A blended film characterized in that, The polypropylene and the cyclic olefin copolymer are blended without crosslinking agent and compatibilizer, the content of the polypropylene is 70-99wt%, and the content of the cyclic olefin copolymer is 1-30wt%. The cyclic olefin copolymer is a binary random copolymer containing 30-60mol% of A segment and 40-70mol% of X segment, and the X segment is B segment, C segment, D segment, E segment or F segment. Or a ternary random copolymer containing 30-60mol% of A segment, 1-69mol% of B segment and 1-69mol% of Y segment, and the Y segment is C segment, D segment, E segment or F segment. Or a ternary random copolymer containing 15-59mol% of A segment, 40-70mol% of X segment and 1-45mol% of Z segment, and the Z segment is G segment or H segment. The structural formula of A segment to H segment is as follows: 、 、 、 、 、 、 、 ； In the formula, * represents the position of the segment connecting to the polymer main chain, and a is an integer from 1 to 17.

2. The blend film according to claim 1, wherein The melting point of the polypropylene is 155-170℃, and the melt index is 2-10g / 10min.

3. The blend film according to claim 1, wherein The thickness of the blended film is 2-15μm, the heat distortion temperature is 150-168℃, and the heat shrinkage rate in both transverse and longitudinal directions is not more than 3%.

4. The blend film according to claim 1, wherein The number average molecular weight of the cyclic olefin copolymer is 5-1000kg / mol, the molecular weight distribution index is 1.1-6.0, the mr value of the propylene segment is 0.1-1.0, the glass transition temperature is 150-240℃, and the thermal decomposition temperature is above 380℃.

5. The blend film according to claim 1, wherein The preparation method of the cyclic olefin copolymer is as follows: under the protection of nitrogen or inert gas, the reaction monomers are dissolved in an organic solvent, a catalytic system is added to initiate the polymerization reaction, and then a anti-solvent is added to precipitate the product, thereby obtaining the cyclic olefin copolymer. The reaction monomers are a mixture of A monomers and X monomers, or the reaction monomers are a mixture of A monomers, B monomers and Y monomers, or the reaction monomers are a mixture of A monomers, X monomers and Z monomers. The A monomers are the reaction monomers corresponding to the A segment, the X monomers are the reaction monomers corresponding to the X segment, the B monomers are the reaction monomers corresponding to the B segment, the Y monomers are the reaction monomers corresponding to the Y segment, and the Z monomers are the reaction monomers corresponding to the Z segment. The catalytic system includes a main catalyst, and the main catalyst is a half-moly titanium metal catalyst or a double-moly zirconium metal catalyst.

6. The blend film according to claim 5, wherein The molar ratio of the reaction monomers to the main catalyst is 2000:1-20000:1; the polymerization reaction time is 1-180min, and the temperature is 0-150℃.

7. The blend film according to claim 5, wherein The catalytic system further includes a co-catalyst; the co-catalyst is an aluminum-containing compound, and the molar ratio of the aluminum-containing compound to the main catalyst is 10:1-1000:1; or the co-catalyst is a boron-containing compound, and the molar ratio of the boron-containing compound to the main catalyst is 1.0:1-1.5:

1.

8. A method of making a blend film as claimed in any one of claims 1 to 7 characterised in that, First, the polypropylene and the cyclic olefin copolymer are melted and extruded to obtain a base film, and then the base film is subjected to bidirectional stretching and heat setting treatment in sequence, thereby obtaining the blended film, and the process parameters include: the melting temperature is 230-270℃, the thickness of the base film is 25-135μm, the transverse stretching multiple is 2-8 times, the longitudinal stretching multiple is 2-8 times, and the heat setting treatment temperature is 160-180℃.

Images