CN108864518B

CN108864518B - Antistatic brominated butyl rubber/polypropylene thermoplastic elastomer and composition, preparation method and application thereof

Info

Publication number: CN108864518B
Application number: CN201710343572.3A
Authority: CN
Inventors: 李洪真; 王超; 吕鹏飞; 吴卫东
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-05-16
Filing date: 2017-05-16
Publication date: 2021-02-05
Anticipated expiration: 2037-05-16
Also published as: CN108864518A

Abstract

The invention relates to the field of butyl rubber, in particular to an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer, a composition thereof, a preparation method and application thereof. The composition contains brominated butyl rubber, polypropylene and an antistatic agent, wherein: the content of the polypropylene is 30-100 parts by weight and the content of the antistatic agent is 5-20 parts by weight relative to 100 parts by weight of the brominated butyl rubber; the antistatic agent is a carbonaceous material. The composition can form the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer with appropriate surface resistivity, has appropriate mechanical properties, and is favorable for being used as a rubber plug, a combined cover, a gasket and other medical packaging materials.

Description

Antistatic brominated butyl rubber/polypropylene thermoplastic elastomer and composition, preparation method and application thereof

Technical Field

The invention relates to the field of butyl rubber, in particular to an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer, a composition thereof, a preparation method and application thereof.

Background

The brominated butyl rubber/polypropylene thermoplastic elastomer is prepared by dynamic vulcanization reaction technology of brominated butyl rubber and polypropylene, has excellent elasticity and sealing property, can be subjected to thermoplastic forming processing and recycling circulation, can form materials such as rubber plugs, combined covers, gaskets and the like for medicine packaging, and is a safe and reliable novel thermoplastic elastomer. Since medical packaging materials such as rubber plugs and the like are in direct contact with medicines, the control of particles on the surfaces of the packaging materials is very important, and the electrostatic adsorption of the packaging materials influences the cleanliness of the surfaces of the packaging materials.

Disclosure of Invention

The invention aims to solve the problem that the existing medical packaging material formed by brominated butyl rubber/polypropylene thermoplastic elastomer is easily polluted by electrostatic adsorption, and provides an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer capable of reducing the surface electrostatic adsorption, a composition thereof, a preparation method thereof and application thereof.

In order to achieve the above object, the present invention provides an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer composition comprising a brominated butyl rubber, a polypropylene and an antistatic agent, wherein:

the content of the polypropylene is 30-100 parts by weight and the content of the antistatic agent is 5-20 parts by weight relative to 100 parts by weight of the brominated butyl rubber; the antistatic agent is a carbonaceous material.

The invention also provides an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer formed by the composition.

The invention provides a preparation method of an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer, which comprises the following steps: the above-mentioned composition is mixed and extruded to make granules.

The invention also provides the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer prepared by the method.

The invention also provides a medical packaging material formed by the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer.

The invention also provides application of the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer as a medical packaging material.

The composition can form the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer with appropriate surface resistivity, has appropriate mechanical properties, and is favorable for being used as a rubber plug, a combined cover, a gasket and other medical packaging materials.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer composition, which contains brominated butyl rubber, polypropylene and an antistatic agent, wherein:

According to the invention, the carbonaceous material is contained in the composition as the antistatic agent, and the brominated butyl rubber and the polypropylene are subjected to certain orientation arrangement in the melt vulcanization process, so that the surface resistivity of the obtained antistatic brominated butyl rubber/polypropylene thermoplastic elastomer meets the requirement. Although the brominated butyl rubber, the polypropylene and the antistatic agent are controlled to satisfy the above content ranges in the present invention to obtain the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer having the surface resistivity satisfying the requirement, it is preferable that the content of the polypropylene is 40 to 80 parts by weight and the content of the antistatic agent is 5 to 15 parts by weight with respect to 100 parts by weight of the brominated butyl rubber in consideration of the surface resistivity, the mechanical properties and the particularity of the medical encapsulating material. More preferably, the polypropylene is contained in an amount of 50 to 70 parts by weight and the antistatic agent is contained in an amount of 6 to 12 parts by weight, relative to 100 parts by weight of the brominated butyl rubber.

The carbonaceous material refers to an elemental carbonaceous material having an electrical conductivity, and various elemental carbonaceous materials capable of achieving the above effects, which are conventional in the art, can be adopted, such as one or more of carbon black, graphite and carbon nanomaterials. However, in order to be better compatible with antistatic brominated butyl rubber/polypropylene, in order to obtain an elastomer more suitable as a medical encapsulating material, preferably the carbonaceous material is a high structure carbon black.

According to the present invention, the particle size of the carbonaceous material can be varied within a wide range, and it is preferable to use a carbonaceous material having a small particle size. Preferably, the carbonaceous material has a particle size of 10-100nm, preferably 20-60nm, more preferably 30-40 nm.

According to the present invention, the carbonaceous material may be selected to have a specific resistivity so as to obtain a more excellent antistatic effect, and it is preferable to use a carbonaceous material having a lower resistivity. In particular, a carbonaceous material having a resistivity of 5. omega. cm or less, preferably 1. omega. cm or less, more preferably 0.1 to 0.6. omega. cm.

According to the present invention, the brominated butyl rubber may be various brominated butyl rubbers conventionally used in the art, but it is preferable to use brominated butyl rubbers which meet medical requirements, for example, brominated butyl rubbers having a volatile content of 1% by weight or less, preferably 0.8% by weight or less (more preferably 0.05 to 0.5% by weight) or less. Preferably, the ash content of the brominated butyl rubber is 1 wt% or less, preferably 0.8 wt% or less, more preferably 0.05 to 0.8 wt%.

More preferably, the brominated butyl rubber has a number average molecular weight of 100,000 to 500,000. Preferably, the bromine is present in an amount of 0.5 to 2.5 wt.%, based on the total weight of the brominated butyl rubber.

According to the present invention, the brominated butyl rubber may be various polypropylenes conventionally used in the art, but it is preferable to use a polypropylene that meets medical requirements, particularly a polypropylene having a crystallinity of 50% or more, preferably 85 to 98%. In view of the fact that a suitable melt index has an important effect on the processability and compatibility of the elastomer, it is preferred that the polypropylene has a melt index of 1 to 15g/10min, preferably 1 to 10g/10 min.

In a preferred embodiment of the present invention, the polypropylene has a number average molecular weight of 10,000 to 500,000, more preferably 50,000 to 250,000.

In order to form an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer by vulcanization according to the present invention, the composition typically also contains a vulcanizing agent. The vulcanizing agent may be any vulcanizing agent conventionally used in the art for vulcanizing brominated butyl rubber/polypropylene elastomers, but in view of the advantages of good heat resistance, compression set and non-coloring of products using an organic peroxide vulcanization system, it is preferable that the vulcanizing agent is an organic peroxide, more preferably dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 1, 4-bis (t-butylperoxydiisopropyl) benzene, 1, 3-bis (t-butylperoxydiisopropyl) benzene, 2, 5-dimethyl-2, 5- (di-t-butylperoxy) -3-hexyne, ethyl-3, 3-bis (t-butylperoxy) butyrate, ethyl-3, 3-di (t-amylperoxy) butyrate, dibenzoyl peroxide, 1-di-t-butylperoxy-3, 3, 5-trimethylcyclohexane, 1-di (t-butylperoxy) cyclohexane, 1-di (t-amylperoxy) cyclohexane, and t-butylperoxybenzoate.

According to the invention, the amount of vulcanizing agent used may vary within wide limits, and in order to obtain a thermoplastic elastomer suitable as a pharmaceutical encapsulating material, the vulcanizing agent is preferably present in an amount of 1 to 15 parts by weight, preferably 1.5 to 10 parts by weight, relative to 100 parts by weight of brominated butyl rubber.

According to the present invention, in order to improve the durability of the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer, the composition may further contain an antioxidant. The antioxidant may be various antioxidants conventionally used in the art, but in view of the antistatic property and the medical material general purpose of the present invention, preferably, the antioxidant is one or more of hindered phenolic antioxidants and phosphite antioxidants, more preferably a combination of hindered phenolic antioxidants and phosphite antioxidants, and particularly preferably a mixture of hindered phenolic antioxidants and phosphite antioxidants in a weight ratio of 1: 0.5-5, preferably 1: 1-3 of a combination of a hindered phenol antioxidant and a phosphite antioxidant. By combining the hindered phenol antioxidant and the phosphite antioxidant, the effects of good effect, good comprehensive performance and full synergistic effect of various additives can be obtained.

Wherein, preferably, the hindered phenol antioxidant is one or more of antioxidant 245, antioxidant 264, antioxidant 300, antioxidant 1076, antioxidant 1010, antioxidant 1098, antioxidant 1425, antioxidant 2246, antioxidant KY-586, antioxidant 1135, antioxidant 1035, antioxidant 3114 and antioxidant 1520.

Wherein, the phosphite antioxidant is preferably one or more of antioxidant 168, antioxidant TNP, antioxidant 242, antioxidant 626 and antioxidant 618.

In a preferred embodiment of the present invention, the antioxidant is a combination of antioxidant 1010 and antioxidant 168.

According to the present invention, the content of the antioxidant may vary within a wide range as long as the desired antioxidant effect can be obtained, and preferably, the content of the antioxidant is 0.5 to 5 parts by weight, preferably 1 to 2 parts by weight, relative to 100 parts by weight of the brominated butyl rubber.

According to the invention, the composition may also contain other auxiliaries, such as softeners and/or lubricants.

The softener has the functions of improving the plasticity of the rubber compound, reducing the viscosity of the rubber compound and the temperature during mixing, and can be one or more of liquid paraffin, paraffin oil, naphthenic oil, white oil and rubber oil. The softener may be used in an amount of, for example, 1 to 15 parts by weight, preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the brominated butyl rubber.

Wherein the lubricant has the functions of improving rubber processing fluidity and demoulding performance, reducing torque and reducing equipment friction, and can be one or more of stearic acid, polyethylene wax, barium stearate, lead stearate and zinc stearate. The lubricant may be used, for example, in an amount of 1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the brominated butyl rubber.

The amount of the aid used according to the present invention may be suitably adjusted depending on the desired properties, and is preferably 1 to 20 parts by weight, preferably 1 to 5 parts by weight, relative to 100 parts by weight of the brominated butyl rubber.

The invention also provides an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer formed by the composition. The elastomer forming method is not particularly limited, and any elastomer may be used or may contain the active ingredient of the composition of the present invention.

The invention also provides a preparation method of the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer, which comprises the following steps: the above-mentioned composition is mixed and extruded to make granules.

According to the present invention, the composition may be mixed, either stepwise or by mixing the components of the composition together, and the present invention is not particularly limited thereto, and the mixing conditions are not limited as long as the composition can be sufficiently mixed, for example, in a high-speed mixer for 2 to 5 minutes.

According to the present invention, the extrusion granulation may be performed by feeding the above mixed mixture to a screw machine, and the conditions for extrusion granulation may also be the conditions for preparing the brominated butyl rubber/polypropylene thermoplastic elastomer, which are conventional in the art, for example, the conditions for extrusion granulation include: the rotation speed of the screw machine is 120-600 r/min, and the temperature is 140-200 ℃.

The medical packaging material can be, for example, a rubber plug, a combined cover, a gasket, a sealing ring and the like.

The antistatic brominated butyl rubber/polypropylene thermoplastic elastomer provided by the invention has good antistatic performance, for example, the surface resistivity of the obtained elastomer can reach more than 200 omega cm, preferably more than 230 omega cm, for example, 210-1200 omega cm, preferably 230-300 omega cm, more preferably 250-290 omega cm; but also has excellent mechanical property, wherein the tensile strength can reach more than 5.7MPa, preferably 6-8.5 MPa; an elongation at break of 650% or more, for example 700% or more, preferably 750% to 920%; the permanent tensile set can reach more than 65%, preferably 70-85%.

The present invention will be described in detail below by way of examples.

Examples 1 to 8

This example illustrates the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer of the present invention, its composition and method of preparation.

According to the formulation shown in Table 1, brominated butyl rubber, polypropylene, an antistatic agent, a vulcanizing agent, an auxiliary agent and an oxidizing agent are put into a high-speed mixer to be mixed for 4min, and then a screw extruder is used for extrusion granulation at 200 ℃ and the screw revolution number of 200 r/min, so that elastomers P1-P8 are obtained.

Wherein the brominated butyl rubber is available from Exxon Mobil corporation grade 2211, the volatile content is 0.1 wt%, the ash content is 0.8 wt%, and the bromine content is 2 wt%;

the polypropylene is purchased from Shanghai Shi chemical company F800EPS, the crystallinity is 95 percent, the melt index is 8g/10min, and the number average molecular weight is 8-15 ten thousand;

the antistatic agent is high-structure carbon black which is purchased from the company VXC72 of Cabot, the granularity is 30nm, and the resistivity is 0.12 omega cm;

the vulcanizing agent is dicumyl peroxide;

the auxiliary agent is prepared from the following components in percentage by weight of 1: 0.2 of liquid paraffin (purchased from national pharmaceutical group chemical agents, ltd.) and stearic acid (purchased from national pharmaceutical group chemical agents, ltd.);

the oxidant is 1: 1 antioxidant 1010 and antioxidant 168.

Example 9

According to the formulation and preparation of elastomer P1, except that the antistatic agent is carbon black available from Cambot corporation under the N330 trademark, with a particle size of 300nm and a resistivity of 10 Ω. cm; thereby obtaining an elastomer P9.

Comparative example 1

According to the formulation and preparation of elastomer P1, except that no antistatic agent was used, elastomer DP1 was obtained.

Comparative example 2

According to the formulation and preparation of elastomer P1, except that 2 parts by weight of antistatic agent were used, elastomer DP2 was obtained.

Comparative example 3

According to the formulation and preparation of elastomer P1, 30 parts by weight of antistatic agent were used, giving elastomer DP 3.

Comparative example 4

According to the formulation and preparation of elastomer P1, 10 parts by weight of polypropylene were used, giving elastomer DP 4.

Comparative example 5

According to the formulation and preparation of elastomer P1, 120 parts by weight of polypropylene were used, giving elastomer DP 5.

TABLE 1

Test example

The tensile strength, elongation at break, tensile set and surface resistivity of the above elastomers P1-P9 and DP1-DP5 were measured, respectively, and the results are shown in Table 2, in which: tensile strength, elongation at break and tensile set were tested according to the method in GB/T528-2009. The surface resistivity was tested according to the method in GB/T1410-2006.

TABLE 2

As can be seen from Table 2, the elastomer obtained by using the composition of the present invention can obtain suitable surface resistivity, tensile strength, elongation at break and tensile permanent deformation, thereby showing that the elastomer obtained by using the composition of the present invention has excellent mechanical properties and good electrical conductivity.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. An antistatic brominated butyl rubber/polypropylene thermoplastic elastomer composition comprising a brominated butyl rubber, a polypropylene and an antistatic agent, wherein:

the content of the polypropylene is 30-100 parts by weight and the content of the antistatic agent is 5-20 parts by weight relative to 100 parts by weight of the brominated butyl rubber; the antistatic agent is high-structure carbon black;

the crystallinity of the polypropylene is 85-98%;

the composition also contains a vulcanizing agent which is an organic peroxide; the vulcanizing agent is contained in an amount of 1 to 15 parts by weight relative to 100 parts by weight of the brominated butyl rubber;

the surface resistivity of the composition is 210-310. omega. cm.

2. The composition according to claim 1, wherein the polypropylene is contained in an amount of 40 to 80 parts by weight and the antistatic agent is contained in an amount of 5 to 15 parts by weight, relative to 100 parts by weight of the brominated butyl rubber.

3. The composition according to claim 2, wherein the polypropylene is contained in an amount of 50 to 70 parts by weight and the antistatic agent is contained in an amount of 6 to 12 parts by weight, relative to 100 parts by weight of the brominated butyl rubber.

4. The composition of any of claims 1-3, wherein the high structure carbon black has a particle size of 10-100 nm.

5. The composition of claim 4, wherein the high structure carbon black has a particle size of 20-60 nm.

6. The composition of claim 5, wherein the high structure carbon black has a particle size of 30-40 nm.

7. The composition according to any one of claims 1 to 3, wherein the high structure carbon black has a resistivity of 5 Ω -cm or less.

8. The composition according to claim 7, wherein the high structure carbon black has a resistivity of 1 Ω -cm or less.

9. The composition of claim 8, wherein the high structure carbon black has a resistivity of 0.1 to 0.6 Ω -cm.

10. The composition of any of claims 1-3, wherein the brominated butyl rubber has a volatiles content of 1 wt.% or less.

11. The composition of claim 10, wherein the brominated butyl rubber has a volatiles content of 0.8 wt.% or less.

12. The composition of any of claims 1-3, wherein the brominated butyl rubber has an ash content of 1 wt% or less.

13. The composition of claim 12, wherein the brominated butyl rubber has an ash content of 0.8 wt% or less.

14. The composition according to any one of claims 1 to 3, wherein the polypropylene has a melt index of 1 to 15g/10 min.

15. The composition of claim 14, wherein the polypropylene has a melt index of 1-10g/10 min.

16. The composition according to any one of claims 1 to 3, wherein the organic peroxide is dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 1, 4-bis (t-butylperoxydiisopropyl) benzene, 1, 3-bis (t-butylperoxydiisopropyl) benzene, 2, 5-dimethyl-2, 5- (di-t-butylperoxy) -3-hexyne, ethyl-3, 3-bis (t-butylperoxy) butyrate, ethyl-3, 3-bis (t-amylperoxy) butyrate, dibenzoyl peroxide, 1-di-t-butylperoxy-3, 3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, 1, 1-di (t-amyl peroxy) cyclohexane and t-butyl peroxybenzoate.

17. The composition according to claim 16, wherein the vulcanizing agent is contained in an amount of 1.5 to 10 parts by weight relative to 100 parts by weight of the brominated butyl rubber.

18. The composition of any one of claims 1-3, wherein the composition further comprises an antioxidant, wherein the antioxidant is one or more of a hindered phenol antioxidant and a phosphite antioxidant.

19. The composition of claim 18, wherein the antioxidant is a combination of hindered phenolic antioxidants and phosphite antioxidants.

20. The composition of claim 19, wherein the weight ratio of hindered phenolic antioxidant to phosphite antioxidant is 1: 0.5-5.

21. The composition of claim 20, wherein the weight ratio of hindered phenolic antioxidant to phosphite antioxidant is 1: 1-3.

22. The composition of claim 18, wherein the hindered phenolic antioxidant is one or more of antioxidant 245, antioxidant 264, antioxidant 300, antioxidant 1076, antioxidant 1010, antioxidant 1098, antioxidant 1425, antioxidant 2246, antioxidant KY-586, antioxidant 1135, antioxidant 1035, antioxidant 3114, and antioxidant 1520; the phosphite antioxidant is one or more of antioxidant 168, antioxidant TNP, antioxidant 242, antioxidant 626 and antioxidant 618.

23. The composition of claim 18, wherein the antioxidant is present in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the brominated butyl rubber.

24. The composition of claim 23, wherein the antioxidant is present in an amount of 1 to 2 parts by weight per 100 parts by weight of the brominated butyl rubber.

25. The composition according to any one of claims 1 to 3, wherein the composition further comprises an auxiliary agent, and the auxiliary agent is a softener and/or a lubricant.

26. The composition of claim 25, the softening agent is one or more of liquid paraffin, paraffin oil, naphthenic oil, white oil, and rubber oil; the lubricant is one or more of stearic acid, polyethylene wax, barium stearate, lead stearate and zinc stearate.

27. The composition of claim 25, wherein the adjuvant is present in an amount of 1 to 20 parts by weight per 100 parts by weight of the brominated butyl rubber.

28. The composition of claim 27, wherein the adjuvant is present in an amount of 1 to 5 parts by weight per 100 parts by weight of the brominated butyl rubber.

29. An antistatic brominated butyl rubber/polypropylene thermoplastic elastomer formed from the composition of any one of claims 1-28.

30. A method for preparing an antistatic brominated butyl rubber/polypropylene thermoplastic elastomer, which comprises the following steps: mixing and extrusion granulating a composition according to any one of claims 1 to 28.

31. The method of claim 30, wherein the conditions of the extrusion granulation comprise: the rotation speed of the screw machine is 120-600 r/min, and the temperature is 140-200 ℃.

32. An antistatic brominated butyl rubber/polypropylene thermoplastic elastomer made by the process of claim 30 or 31.

33. A pharmaceutical packaging material formed from the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer of claim 29 or 32.

34. Use of the antistatic brominated butyl rubber/polypropylene thermoplastic elastomer of claim 29 or 32 as a pharmaceutical packaging material.