CN113308082A - Functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition and preparation method thereof - Google Patents
Functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a functionalized solution polymerized styrene-butadiene rubber modified C5 petroleum resin composition and a preparation method thereof. Mainly aiming at the problems that the variety of monomers modified by C5 petroleum resin is less, the variety of C5 petroleum resin products with good polarity or functionality is single, and the like, the functional solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition is provided, and the preparation method is to mix the functional solution-polymerized styrene-butadiene rubber and the C5 petroleum resin according to a certain mass ratio to obtain the functional solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition. The obtained functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition can improve the bonding property of the solution-polymerized styrene-butadiene rubber, the quality of the C5 petroleum resin and styrene-butadiene rubber products is obviously improved, the preparation process is simple, the performance is stable, the composition can be widely applied to the fields of adhesives, sealing, coatings, printing ink and the like, and the application field of the composition is greatly widened.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition and a preparation method thereof.
Background
The C5 petroleum resin is a thermoplastic resin obtained by polymerizing a C5 fraction, which is a by-product of a device for producing ethylene by cracking, as a main raw material in the presence of a catalyst or copolymerizing the fraction with an acid anhydride, a phenol compound or an aromatic hydrocarbon compound. The C5 petroleum resin has good viscosity increasing property, heat resistance, stability, water resistance and acid and alkali resistance, is mainly used in the fields of adhesives, sealing, printing ink, coating and the like, and has large market demand.
The C5 petroleum resin has good compatibility with phenolic resin, terpene resin, coumarone resin, natural rubber, synthetic rubber, etc. However, the C5 petroleum resin lacks polar groups in its molecular structure and is poorly compatible with polar polymers, thus limiting its effective use. In addition, the C5 petroleum resin has the problems of small relative molecular weight, low softening point, relatively poor thermal stability, strength and corrosion resistance and the like, and greatly limits the application range of the C5 petroleum resin.
The modified petroleum resin is the development direction of C5 petroleum resin and the footing of many new materials, and at present, the modification of petroleum resin mainly has two types. The first is that modifier such as light olefin, aromatic unsaturated hydrocarbon and alicyclic hydrocarbon is added into C5 petroleum resin to improve the solubility, color and stability of the product; the second kind is to graft copolymerization modify with polar group monomer to prepare special petroleum resin with functional group. At present, the types of monomers which can be used for modifying the C5 petroleum resin are few, the types of C5 petroleum resin products with good polarity or functionality are single, the application range of the C5 petroleum resin is limited, and the processing and utilization efficiency of petroleum byproducts is low. How to develop and prepare the modified C5 petroleum resin with high polarity and good functionality will expand the application field of C5 petroleum resin greatly, and has very good application prospect and economic use value.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition and a preparation method thereof, the functionalized solution-polymerized styrene-butadiene rubber and C5 petroleum resin are blended and internally mixed to prepare the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition, and the preparation method has mild preparation conditions, simple process and stable product performance and is suitable for industrial production.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
in a first aspect, the invention provides a functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition, which is a blend of functionalized solution-polymerized styrene-butadiene rubber and C5 petroleum resin, wherein the mass fraction of the functionalized solution-polymerized styrene-butadiene rubber is 3-40 parts, and the balance is C5 petroleum resin, based on 100 parts of the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition;
the C5 petroleum resin is thermoplastic resin prepared by using a byproduct C5 fraction of a cracking ethylene preparation device as a main raw material; the number average molecular weight of the C5 petroleum resin is 100-3000;
the functionalized solution polymerized styrene-butadiene rubber is a terpolymer of butadiene, styrene and diphenylethylene derivatives containing functional groups; the number average molecular weight of the functionalized solution-polymerized styrene-butadiene rubber is 500-30000; the terpolymer contains 0.1-10 wt% of diphenylethylene derivative containing functional groups, 50-90 wt% of butadiene and the balance of styrene;
the diphenylethylene derivative containing functional groups comprises at least one of a silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative, an amino group-containing monomer 1, 1-diphenylethylene derivative and a silicon-oxygen group-and amino group-containing monomer 1, 1-diphenylethylene derivative.
Further, the mass fraction of the functionalized solution-polymerized styrene-butadiene rubber is 5-35 parts, and the balance is C5 petroleum resin, based on 100 parts of the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition.
Further, the molecular weight of the C5 petroleum resin is 200-2500.
Further, the number average molecular weight of the functionalized solution-polymerized styrene-butadiene rubber is 10000-.
Furthermore, the content of the diphenylethylene derivative containing functional groups in the functionalized solution-polymerized styrene-butadiene rubber is 0.5-7 wt%, and the content of butadiene is 55-80 wt%.
Furthermore, the content of the diphenylethylene derivative containing functional groups in the functionalized solution-polymerized styrene-butadiene rubber is 3-5 wt%, and the content of butadiene is 60-70 wt%.
Furthermore, the functionalized solution polymerized styrene-butadiene rubber is a terpolymer of butadiene, styrene and diphenylethylene derivatives containing functional groups, and the glass transition temperature of the terpolymer is-100 ℃ to-50 ℃.
The C5 petroleum resin is a thermoplastic resin obtained by polymerizing a C5 fraction, which is a by-product of a cracking apparatus for producing ethylene, as a main raw material under the presence of a catalyst, or copolymerizing the same with an acid anhydride, a phenol compound or an aromatic hydrocarbon compound.
Further, the C5 petroleum resin includes at least 1 of aliphatic C5 petroleum resin, hydrogenated C5 petroleum resin, mixed C5 petroleum resin.
Further, the chain end or chain of the functionalized solution-polymerized styrene-butadiene rubber terpolymer contains one of a monomer 1, 1-diphenylethylene derivative containing a silicon-oxygen group, a monomer 1, 1-diphenylethylene derivative containing an amino group, and a monomer 1, 1-diphenylethylene derivative containing a silicon-oxygen group and an amino group.
On the other hand, the invention provides a preparation method of the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition, which comprises the following steps of mixing the functionalized solution-polymerized styrene-butadiene rubber and C5 petroleum resin according to the mass ratio of 1: (1.5-40), adding the mixture into an internal mixer at a torque of 40-100rpm, and carrying out internal mixing at a temperature of 80-200 ℃ for 5-30min to obtain the functionalized solution polymerized styrene-butadiene rubber modified C5 petroleum resin composition.
Further, the functionalized solution polymerized styrene-butadiene rubber and the C5 petroleum resin are mixed according to the mass ratio of 1: (2-30), setting the torque to be 40-80rpm, and carrying out internal mixing for 10-20min at the internal mixing temperature of 100-180 ℃, wherein the content of the diphenylethylene derivative containing the functional group in the functionalized solution-polymerized styrene-butadiene rubber is 5-6 wt%, and the content of the butadiene is 60-70 wt%.
Further, the functionalized solution polymerized styrene-butadiene rubber and the C5 petroleum resin are mixed according to the mass ratio of 1: 4, setting the torque to be 60rpm, and carrying out internal mixing for 15min at the internal mixing temperature of 120-160 ℃, wherein the content of the diphenylethylene derivative containing the functional group in the functionalized solution-polymerized styrene-butadiene rubber is 5 wt%, and the content of the butadiene is 70 wt%.
Further, the initial viscosity of the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition is 1-15 cm.
The invention has the beneficial effects that:
the modified C5 petroleum resin by adopting the functionalized solution polymerized styrene-butadiene rubber can obviously improve the polarity of the modified rubber material of the C5 petroleum resin, further improve the compatibility and the dispersibility of the modified rubber material with polar compounds, effectively improve the brittleness of the C5 petroleum resin, and has the advantages of simple preparation process and stable performance. The modified C5 petroleum resin prepared by the method has the advantages of strong polarity and good cohesiveness besides the traditional advantages of the C5 petroleum resin, can be widely applied to the fields of adhesives, coatings, sealing, printing ink and the like, greatly expands the application field of the C5 petroleum resin, and effectively expands the application range of the styrene butadiene rubber.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified; the operations involved are those conventional in the art unless otherwise specified.
According to the embodiment of the invention, a nuclear magnetic resonance spectrometer and an infrared spectrometer are used for analyzing the composition sequence distribution and the microstructure of the copolymer, and a gel permeation chromatograph is used for analyzing the molecular weight and the molecular weight distribution index of the copolymer. The permanent adhesion in the embodiment of the invention is measured by adopting a permanent adhesion tester according to the GB/T4851-1998 standard; the 180 DEG peel strength was measured by a universal peeling machine in accordance with GB/T2792-1998.
Example 1
Functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 30000, wherein the content of butadiene is 55 wt%, the content of the silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative is 3 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-55 ℃. C5 petroleum resin (self-made in laboratory): the molecular weight is 2500. And (3) putting 20 parts of the functional solution-polymerized styrene-butadiene rubber and 80 parts of C5 petroleum resin into an internal mixer, wherein the internal mixing time is 30min, the internal mixing temperature is 180 ℃, and the torque is 40rpm, so as to obtain the functional solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition. The adhesion force of the functionalized modified C5 petroleum resin reaches 15/h, the 180-degree peel strength is 0.8kN/m, and the adhesion force is increased by 2-3 times compared with that of an unmodified matrix resin material.
Example 2
Functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 5000, wherein the content of butadiene is 90 wt%, the content of the monomer 1, 1-diphenylethylene derivative containing the silicon-oxygen group and the amino group is 0.1 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-90 ℃. C5 petroleum resin (self-made in laboratory): the molecular weight is 1000. And (3) putting 40 parts of the functional solution-polymerized styrene-butadiene rubber and 60 parts of C5 petroleum resin into an internal mixer, wherein the internal mixing time is 20min, the internal mixing temperature is 120 ℃, and the torque is 60rpm, so as to obtain the functional solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition. The adhesion force of the functionalized modified C5 petroleum resin reaches 20/h, the 180-degree peel strength is 1.6kN/m, and the adhesion force is increased by 5-6 times compared with that of an unmodified matrix resin material.
Example 3
Functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 15000, wherein the content of butadiene is 70 wt%, the content of amino group-containing monomer 1, 1-diphenylethylene derivatives is 5 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-70 ℃. C5 petroleum resin (self-made in laboratory): the molecular weight is 2000. 10 parts of functionalized solution-polymerized styrene-butadiene rubber and 90 parts of C5 petroleum resin are put into an internal mixer, the internal mixing time is 20min, the internal mixing temperature is 140 ℃, and the torque is 60rpm, so that the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition is obtained. The adhesion force of the functionalized modified C5 petroleum resin reaches 13/h, the 180-degree peel strength is 0.8kN/m, and the adhesion force is increased by 2-3 times compared with that of an unmodified matrix resin material.
Example 4
Functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 15000, wherein the content of butadiene is 70 wt%, the content of the silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative is 5 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-70 ℃. C5 petroleum resin (self-made in laboratory): the molecular weight is 1000. Placing 15 parts of functionalized solution-polymerized styrene-butadiene rubber and 85 parts of C5 petroleum resin into an internal mixer, wherein the internal mixing time is 5min, the internal mixing temperature is 200 ℃, and the torque is 60rpm, so as to obtain the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition. The adhesion force of the functionalized modified C5 petroleum resin reaches 16/h, and the 180-degree peel strength of the functionalized modified C5 petroleum resin is 0.8kN/m, which is 2-3 times higher than that of an unmodified matrix resin material.
Example 5
Functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 15000, wherein the content of butadiene is 70 wt%, the content of the amino group-containing monomer 1, 1-diphenylethylene derivative is 5 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-70 ℃. C5 petroleum resin (self-made in laboratory): the molecular weight is 500. And (3) putting 30 parts of the functional solution-polymerized styrene-butadiene rubber and 70 parts of C5 petroleum resin into an internal mixer, wherein the internal mixing time is 15min, the internal mixing temperature is 200 ℃, and the torque is 60rpm, so as to obtain the functional solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition. The adhesion force of the functionalized modified C5 petroleum resin reaches 14/h, and the 180-degree peel strength of the functionalized modified C5 petroleum resin is 0.8kN/m, which is 2-3 times higher than that of an unmodified matrix resin material.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition is characterized in that the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition is a blend of functionalized solution-polymerized styrene-butadiene rubber and C5 petroleum resin, and the mass fraction of the functionalized solution-polymerized styrene-butadiene rubber is 3-40 parts, and the balance is C5 petroleum resin, based on 100 parts of the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition;
the C5 petroleum resin is thermoplastic resin prepared by using a byproduct C5 fraction of a cracking ethylene preparation device as a main raw material; the number average molecular weight of the C5 petroleum resin is 100-3000.
The functionalized solution polymerized styrene-butadiene rubber is a terpolymer of butadiene, styrene and diphenylethylene derivatives containing functionalized groups; the number average molecular weight of the functionalized solution-polymerized styrene-butadiene rubber is 500-30000; the terpolymer contains 0.1-10 wt% of diphenylethylene derivative containing functional groups, 50-90 wt% of butadiene and the balance of styrene; the diphenylethylene derivative containing functional groups comprises one or more of a silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative, an amino group-containing monomer 1, 1-diphenylethylene derivative and a silicon-oxygen group-and amino group-containing monomer 1, 1-diphenylethylene derivative.
2. The functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition according to claim 1, wherein the C5 petroleum resin is a thermoplastic resin prepared by polymerizing a C5 fraction, which is a by-product of a cracking ethylene production plant, as a main raw material under the condition of a catalyst, or copolymerizing the C5 petroleum resin with an acid anhydride compound, a phenol compound or an aromatic hydrocarbon compound.
3. The functionalized solution-polymerized styrene-butadiene rubber-modified C5 petroleum resin composition according to claim 2, wherein the C5 petroleum resin comprises at least 1 of aliphatic C5 petroleum resin, hydrogenated C5 petroleum resin, and mixed C5 petroleum resin.
4. The functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition according to claim 1, wherein the mass fraction of the functionalized solution-polymerized styrene-butadiene rubber is 5-35 parts, and the balance is C5 petroleum resin, based on 100 parts of the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition.
5. The functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition as claimed in claim 3, wherein the molecular weight of the C5 petroleum resin is 500-2500; the number average molecular weight of the functionalized solution-polymerized styrene-butadiene rubber is 10000-15000.
6. The functionalized solution-polymerized styrene-butadiene rubber-modified C5 petroleum resin composition according to claim 1, wherein the functionalized solution-polymerized styrene-butadiene rubber contains 0.5-7 wt% of diphenylethylene derivatives containing functional groups and 55-80 wt% of butadiene; more preferably, the functionalized solution-polymerized styrene-butadiene rubber contains 3 to 5 weight percent of diphenylethylene derivatives containing functional groups and 60 to 70 weight percent of butadiene.
7. The functionalized solution-polymerized styrene-butadiene rubber-modified C5 petroleum resin composition according to claim 6, wherein the functionalized solution-polymerized styrene-butadiene rubber contains at least one of siloxy group monomer 1, 1-diphenylethylene derivative, amino group-containing monomer 1, 1-diphenylethylene derivative or siloxy group-containing, amino group-containing monomer 1, 1-diphenylethylene derivative monomer at the chain end or in the chain.
8. The preparation method of the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition as claimed in any one of claims 1 to 7, wherein the functionalized solution-polymerized styrene-butadiene rubber and the C5 petroleum resin are mixed according to a mass ratio of 1: (1.5-40), adding the mixture into an internal mixer at a torque of 40-100rpm, and carrying out internal mixing at a temperature of 80-200 ℃ for 5-30min to obtain the functionalized solution polymerized styrene-butadiene rubber modified C5 petroleum resin composition.
9. The method for preparing the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition according to claim 8, wherein the functionalized solution-polymerized styrene-butadiene rubber and the C5 petroleum resin are mixed in a mass ratio of 1: (2-30), setting the torque to be 40-80rpm, and carrying out internal mixing for 10-20min at the internal mixing temperature of 100-180 ℃, wherein the content of the diphenylethylene derivative containing the functional group in the functionalized solution-polymerized styrene-butadiene rubber is 5-6 wt%, and the content of the butadiene is 60-70 wt%.
10. The method for preparing the functionalized solution-polymerized styrene-butadiene rubber modified C5 petroleum resin composition according to claim 9, wherein the functionalized solution-polymerized styrene-butadiene rubber and the C5 petroleum resin are mixed in a mass ratio of 1: 4, setting the torque to be 60rpm, and carrying out internal mixing for 15min at the internal mixing temperature of 120-160 ℃, wherein the content of the diphenylethylene derivative containing the functional group in the functionalized solution-polymerized styrene-butadiene rubber is 5 wt%, and the content of the butadiene is 70 wt%.
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