CN111635466B - Oxazoline-terminated polybutadiene compound and preparation and application thereof - Google Patents
Oxazoline-terminated polybutadiene compound and preparation and application thereof Download PDFInfo
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention belongs to the field of high polymer materials, and mainly relates to an oxazoline-terminated polybutadiene compound, a preparation method thereof and application of the compound as a chain extender in the field of high-valued waste plastics. The oxazoline-terminated polybutadiene compound is prepared by reacting carboxyl-terminated polybutadiene, thionyl chloride and ethanolamine in an organic solvent under a certain condition. The carboxyl-terminated polybutadiene is an elastomer, has a toughening effect, has good compatibility with high impact polystyrene, acrylonitrile-butadiene-styrene copolymer and polypropylene, and oxazoline groups can react with carboxyl generated by aging to realize molecular chain repair and reactive compatibilization. The method has the characteristics of simple operation, mild reaction conditions, high oxazoline group content of the target product oxazoline-terminated polybutadiene oxazoline group, wide application range and the like, is environment-friendly, and has wide application prospect in the field of high-valued waste plastics.
Description
Technical Field
The invention belongs to the field of high polymer materials, and mainly relates to an oxazoline-terminated polybutadiene compound, a preparation method thereof and application of the compound as a chain extender in the field of high-valued waste plastics.
Background
In the synthesis and preparation of polymers, in order to improve the mechanical properties and heat resistance of products, it is an economically feasible method to increase the molecular weight of polymers, and a common method is to add a chain extender and add bifunctional small molecule compounds under blending conditions, such as: bifunctional acid derivatives, isocyanate, anhydride, oxazoline groups, epoxide and the like, wherein the bifunctional compounds react with carboxyl, hydroxyl and amino groups in the polymer to form a bridge between two polymer chains, so that the molecular mass can be directly and obviously increased, the viscosity of a system is improved, and the performance of the product is further improved.
With the large-scale use of plastic products, the use of the plastic products for a short time leads to the great increase of waste plastics, and great harm is caused to the environment and the human health. Therefore, a series of related problems of recycling waste plastics, which are mainly High Impact Polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS) and polypropylene (PP), have attracted intense discussion and attention in academia, and due to aging and breakage of molecular chains and degradation of molecular weight and oxidation of polar groups such as hydroxyl and carboxyl groups, the mechanical properties are deteriorated, especially the impact strength is reduced. Because oxazoline group and carboxyl have strong chemical reaction activity, oxazoline group compounds can be introduced to be used as chain extenders, so that molecular chains can be repaired to achieve the original performance and then reused, polybutadiene can be introduced to increase the compatibility, and further the mechanical property of the polybutadiene is improved.
Disclosure of Invention
The invention aims to provide an oxazoline-terminated polybutadiene compound and a preparation method and application thereof.
The invention is realized by the following technical scheme: an oxazoline-terminated polybutadiene compound, which has a structural formula:
the invention further provides a preparation method of the oxazoline-terminated polybutadiene compound, which comprises the following steps:
(1) dissolving carboxyl-terminated polybutadiene in an organic solvent to obtain a carboxyl-terminated polybutadiene solution;
(2) adding thionyl chloride into a carboxyl-terminated polybutadiene solution, and reacting for 2-3 hours at 40-50 ℃ by magnetic stirring until bubbles stop generating;
(3) adding ethanolamine into the system, stirring and reacting for 2 hours at constant temperature by magnetic force, adding a dehydrating agent, and reacting for 3-12 hours at 110-140 ℃ to obtain the oxazoline terminated polybutadiene compound.
As a further improvement of the technical scheme of the preparation method, the carboxyl-terminated polybutadiene has Mn of 3000-4800 and a carboxylic acid content of 0.5 mmol/g.
As a further improvement of the technical scheme of the preparation method, the molar ratio of the carboxyl-terminated polybutadiene to the ethanolamine is 1 (3-13).
As a further improvement of the technical scheme of the preparation method, the organic solvent is toluene.
As a further improvement of the technical scheme of the preparation method, the dehydrating agent is a 4A molecular sieve.
As a further improvement of the technical scheme of the preparation method, the relative content of oxazolinyl in the prepared oxazoline-terminated polybutadiene compound is 0.8-12.5%.
The invention further provides application of the oxazoline-terminated polybutadiene compound as a chain extender in the recovery modification and reutilization of waste plastics.
The oxazoline-terminated polybutadiene compound adopts carboxyl-terminated polybutadiene (CTPB) and thionyl chloride (SOCl) 2 ) And ethanolamine reacts in an organic solvent under certain conditions to prepare the oxazoline-terminated polybutadiene compound (OTPB). Carboxyl-terminated polybutadiene (CTPB) is an elastomer, has a toughening effect and is compatible with high impact polystyreneAlkene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS) and polypropylene (PP) have good compatibility, and oxazoline groups can react with carboxyl generated by aging to realize molecular chain repair and reactive compatibilization. The method has the characteristics of simple operation, mild reaction conditions, high oxazoline group content in the target product oxazoline-terminated polybutadiene, wide application range and the like, is environment-friendly, and has wide application prospect in the field of high-valued waste plastics.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows an infrared spectrum of the oxazoline terminated polybutadiene compound and the raw material thereof. Wherein a is the infrared spectrum curve of carboxyl-terminated polybutadiene, b is the infrared spectrum curve of oxazoline-terminated polybutadiene compound, and 732cm is arranged in the line a and the line b -1 The characteristic peak of cis-1, 4 double bond is shown in the specification, and the characteristic peak of carbonyl of carboxyl-terminated polybutadiene is 1741cm -1 A position. The line b is 1646cm relative to the line a -1 A new infrared absorption peak appears, and the related group is a stretching vibration peak of-C ═ N-, and the peak can be used as the judgment basis of the oxazoline group, namely the oxazoline group-terminated polybutadiene compound.
FIG. 2 is an ultraviolet spectrum of the oxazoline terminated polybutadiene compound and the raw material thereof. Wherein a is an ultraviolet spectrum curve of carboxyl-terminated polybutadiene, and b is an ultraviolet spectrum curve of oxazoline-terminated polybutadiene compound. Both curves a and b present an absorption peak around 240 — C ═ C-. In the figure, 288nm is a carbonyl pi transition ultraviolet absorption peak in carboxyl, 202nm is a carbonyl N pi transition ultraviolet absorption peak in carboxyl, a curve is shifted relative to b, the peak position is shifted from 288nm to 295nm, namely pi transition of-C-N-, because carboxyl in CTPB is not completely reacted, C-O and-C-N-are mutually interfered and superposed, and the ultraviolet spectrum curve shows red shift.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without making any creative effort, shall fall within the protection scope of the present invention.
The oxazoline terminated polybutadiene compound provided by the invention adopts Carboxyl Terminated Polybutadiene (CTPB) and thionyl chloride (SOCl) 2 ) And ethanolamine reacts in an organic solvent under certain conditions to prepare the oxazoline-terminated polybutadiene compound (OTPB). The specific process for obtaining the oxazoline-terminated polybutadiene compound is as follows:
(1) dissolving carboxyl-terminated polybutadiene in an organic solvent to obtain a carboxyl-terminated polybutadiene solution;
(2) adding thionyl chloride into a carboxyl-terminated polybutadiene solution, and reacting for 2-3 hours at 40-50 ℃ by magnetic stirring until bubbles stop generating;
(3) adding ethanolamine into the system, stirring and reacting for 2 hours at constant temperature by magnetic force, adding a dehydrating agent, and reacting for 3-12 hours at 110-140 ℃ to obtain the oxazoline terminated polybutadiene compound.
In the above technical means, it is preferable that the carboxyl-terminated polybutadiene has Mn of 3000 to 4800 and a carboxylic acid content of 0.5 mmol/g. The carboxyl-terminated polybutadiene can be purchased from Huihong plastics factory of Yuyao City in Zhejiang province. The organic solvent used in the invention can be ethanol, acetone or toluene, and toluene can be preferably used.
In the invention, the molar ratio of the carboxyl-terminated polybutadiene to the ethanolamine is 1 (3-13), and the molar ratio is preferably 1 (5-11), and more preferably 1: 11. According to the invention, after ethanolamine is added into the system, the temperature of magnetic constant-temperature stirring reaction is the same as that in the step (2). In specific implementation, the dehydrating agent used can be any molecular sieve drying agent capable of adsorbing water, and a 4A molecular sieve can be preferably used.
After the dehydrating agent is added in the technical scheme of the invention, the reaction temperature is 110-140 ℃, and the preferable reaction temperature is 120 ℃. Specifically, the reaction time is 3 to 12 hours, preferably 5 to 11 hours, and more preferably 7 to 9 hours.
The invention further provides application of the oxazoline-terminated polybutadiene compound as a chain extender in the recovery modification and reutilization of waste plastics.
The source of the waste plastics is not particularly limited in the present invention, and the waste plastics may be a waste plastics reclaimed material recovered from product wastes. The oxazoline terminated polybutadiene compound can be used as a chain extender and can be particularly applied to R-ABS, waste HIPS, waste PP and the like.
The specific using method of the oxazoline-terminated polybutadiene compound as the chain extender comprises the following steps: the oxazoline terminated polybutadiene compound and the waste plastic are melted, blended, extruded, granulated, dried and then injection molded.
In the specific use method, when R-ABS is adopted as the waste plastic, the temperature of the melt blending is 190-230 ℃. The apparatus used for melt blending extrusion in the present invention is not particularly limited, and a twin-screw extruder and an injection molding machine well known to those skilled in the art are preferable. The detailed technological parameters of the double-screw extruder adopted by the invention are as follows: the temperature of each section from the feed inlet to the machine head is preferably 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 225 ℃, 210 ℃, 200 ℃ and 190 ℃ respectively; the speed of the twin-screw extruder is preferably 60 r/min. The injection molding machine adopted by the invention has the following detailed process parameters: the temperatures from one stage to the nozzle are preferably 220 ℃, 225 ℃, 230 ℃ and 225 ℃ respectively; the injection pressure is 35.0MPa, the pressure maintaining pressure is 45.0MPa, and the flow is 40cm 2 /s。
The oxazoline terminated polybutadiene compound provided by the invention can be used as a chain extender to modify waste plastics to obtain a waste plastics modified material with excellent mechanical properties, especially the impact strength is greatly improved, so that the waste plastics are effectively recycled, the influence of the waste plastics on the environment is greatly reduced, and the waste plastics are enabled to realize high-value.
In order to illustrate the invention more clearly, the following examples are given in detail:
example 1:
(1) weighing 20.42g of carboxyl-terminated polybutadiene, and dissolving in 50ml of toluene to obtain a carboxyl-terminated polybutadiene toluene solution;
(2) slowly adding 4.75g of thionyl chloride into the carboxyl-terminated polybutadiene toluene solution, and magnetically stirring the mixture at the temperature of 40-50 ℃ for reacting for 2-3 hours until bubbles are generated;
(3) adding a certain amount of ethanolamine into the system, magnetically stirring to react for 2 hours, adding a 4A molecular sieve, and reacting for 3 hours at 120 ℃ to obtain the oxazoline terminated polybutadiene compound. Wherein the molar ratio of the added ethanolamine to the carboxyl-terminated polybutadiene is 1: 3.
Example 2:
(1) weighing 20.42g of carboxyl-terminated polybutadiene, and dissolving in 50ml of toluene to obtain a carboxyl-terminated polybutadiene toluene solution;
(2) slowly adding 4.75g of thionyl chloride into the carboxyl-terminated polybutadiene toluene solution, and magnetically stirring the mixture at the temperature of 40-50 ℃ for reacting for 2-3 hours until bubbles are generated;
(3) adding a certain amount of ethanolamine into the system, magnetically stirring to react for 2 hours, adding a 4A molecular sieve, and reacting for 5 hours at 120 ℃ to obtain the oxazoline terminated polybutadiene compound. Wherein the molar ratio of the added ethanolamine to the carboxyl-terminated polybutadiene is 1: 5.
Example 3:
(1) weighing 20.42g of carboxyl-terminated polybutadiene, and dissolving in 50ml of toluene to obtain a carboxyl-terminated polybutadiene toluene solution;
(2) slowly adding 4.75g of thionyl chloride into the carboxyl-terminated polybutadiene toluene solution, and magnetically stirring the mixture at the temperature of 40-50 ℃ to react for 2-3 hours until bubbles stop generating;
(3) adding a certain amount of ethanolamine into the system, magnetically stirring to react for 2 hours, adding a 4A molecular sieve, and reacting for 7 hours at 120 ℃ to obtain the oxazoline terminated polybutadiene compound. Wherein the molar ratio of the added ethanolamine to the carboxyl-terminated polybutadiene is 1: 7.
Example 4:
(1) weighing 20.42g of carboxyl-terminated polybutadiene, and dissolving in 50ml of toluene to obtain a carboxyl-terminated polybutadiene toluene solution;
(2) slowly adding 4.75g of thionyl chloride into the carboxyl-terminated polybutadiene toluene solution, and magnetically stirring the mixture at the temperature of 40-50 ℃ for reacting for 2-3 hours until bubbles are generated;
(3) adding a certain amount of ethanolamine into the system, magnetically stirring to react for 2 hours, adding a 4A molecular sieve, and reacting for 9 hours at 120 ℃ to obtain the oxazoline terminated polybutadiene compound. Wherein the molar ratio of the added ethanolamine to the carboxyl-terminated polybutadiene is 1: 9.
Example 5:
(1) weighing 20.42g of carboxyl-terminated polybutadiene, and dissolving in 50ml of toluene to obtain a carboxyl-terminated polybutadiene toluene solution;
(2) slowly adding 4.75g of thionyl chloride into the carboxyl-terminated polybutadiene toluene solution, and magnetically stirring the mixture at the temperature of 40-50 ℃ for reacting for 2-3 hours until bubbles are generated;
(3) adding a certain amount of ethanolamine into the system, magnetically stirring to react for 2 hours, adding a 4A molecular sieve, and reacting for 11 hours at 120 ℃ to obtain the oxazoline terminated polybutadiene compound. Wherein the molar ratio of the added ethanolamine to the carboxyl-terminated polybutadiene is 1: 11.
Table 1 shows that the relative content of oxazoline groups in the oxazoline-terminated polybutadiene compounds synthesized in example 1, example 2, example 3, example 4 and example 5 was measured, and from Fourier infrared spectral curves of CTPB and oxazoline-terminated polybutadiene, the stretching vibration of-C ═ N-double bond was 1646cm -1 Cis-1, 4 double bond (c) at 732cm -1 According to the reaction mechanism, no by-product containing-C ═ N-group exists in the reaction process, no other raw material or intermediate carries-C ═ N-group, the cis-1, 4 double bond does not participate in the reaction process, and the ratio of the double bond before and after the reaction can be used for representing the relative content of oxazoline group.
The calculation formula of the relative content of oxazoline groups is as follows:
in the formula:
A 1646 represents: -C-N-the integrated area of the characteristic peak on the infrared spectral curve;
A 732 represents: integral area of characteristic peak of cis-1, 4 double bond (c) on infrared spectrum curve;
e represents: relative representation parameters of the oxazoline group content in the oxazoline-terminated polybutadiene.
TABLE 1 comparison of the amount of Ethanolamine used to the relative amount of oxazolinyl groups
| Numbering | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Ethanolamine/carboxyl (molar ratio) | 3 | 5 | 7 | 9 | 11 |
| A 1646 | 0.7620 | 0.2954 | 0.3317 | 0.3932 | 0.4025 |
| A 732 | 0.6112 | 1.7464 | 3.2473 | 4.3557 | 4.9813 |
| E | 0.8021 | 5.9103 | 9.7881 | 11.0765 | 12.375 |
Example 6:
selecting the product with the highest relative content of oxazoline groups in example 5, performing melt blending extrusion on an oxazoline-terminated polybutadiene compound serving as a chain extender and R-ABS, performing granulation drying, and then performing injection molding to test the basic performance (the specific molding process parameters refer to the above description in the specific embodiment), and evaluating the modification effect of the oxazoline-terminated polybutadiene compound (OTPB) serving as the chain extender on the waste plastics. As can be seen from Table 2, the notched impact strength of OTPB/R-ABS increases significantly with the increase of OTPB, which is caused by the reaction of carboxyl group in R-ABS and oxazoline in OTPB, and when the content of OTPB is 9 wt%, OTPB/R-ABS has a maximum notched impact strength of 7.3KJ/m 2 . When the OTPB continues to increase, the toughness is insufficient because the OTPB belongs to low molecular weight rubber, and the notch impact property can be caused by the excessively high contentCan be lowered.
TABLE 2 Effect of oxazoline terminated polybutadiene Compounds as chain extender on modification of R-ABS
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. An oxazoline-terminated polybutadiene, which is characterized in that the structural formula is as follows:
the preparation method of the oxazoline-terminated polybutadiene comprises the following steps:
(1) dissolving carboxyl-terminated polybutadiene in an organic solvent to obtain a carboxyl-terminated polybutadiene solution; the carboxyl-terminated polybutadiene has Mn = 3000-4800;
(2) adding thionyl chloride into a carboxyl-terminated polybutadiene solution, and reacting for 2-3 hours at 40-50 ℃ under magnetic stirring until bubbles stop generating;
(3) adding ethanolamine into the system, stirring and reacting for 2 hours under constant magnetic temperature, adding a 4A molecular sieve, and reacting for 3-12 hours at 110-140 ℃ to obtain the oxazoline terminated polybutadiene compound.
2. The oxazoline-terminated polybutadiene according to claim 1, wherein the carboxyl-terminated polybutadiene has a carboxylic acid content of 0.5 mmol/g.
3. The oxazoline-terminated polybutadiene of claim 1, wherein the molar ratio of the carboxyl-terminated polybutadiene to the ethanolamine is 1 (3-13).
4. The oxazoline-terminated polybutadiene of claim 1, wherein the organic solvent is toluene.
5. The oxazoline-terminated polybutadiene of claim 1, wherein the relative content of oxazoline groups in the oxazoline-terminated polybutadiene is 0.8 to 12.5%.
6. The use of the oxazoline terminated polybutadiene of claim 1 as a chain extender for the recovery, modification and recycling of waste plastics.
7. The use according to claim 6, wherein the waste plastics are waste ABS, waste HIPS or waste PP.
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| US5756621A (en) * | 1995-08-01 | 1998-05-26 | Basf Aktiengesellschaft | 2-oxazolinyl-terminated polymers and oligomers useful as compatibilizers |
| JP2008266543A (en) * | 2007-03-29 | 2008-11-06 | Osaka Univ | Production method of polymer having oxazoline group |
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| JP3219803B2 (en) * | 1991-10-28 | 2001-10-15 | 株式会社日本触媒 | Method for producing oxazoline compound |
| CN108148281B (en) * | 2016-12-05 | 2022-05-06 | 合肥杰事杰新材料股份有限公司 | Low-odor regenerated polypropylene composite material for automobile interior and exterior decoration and preparation method thereof |
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| US5756621A (en) * | 1995-08-01 | 1998-05-26 | Basf Aktiengesellschaft | 2-oxazolinyl-terminated polymers and oligomers useful as compatibilizers |
| JP2008266543A (en) * | 2007-03-29 | 2008-11-06 | Osaka Univ | Production method of polymer having oxazoline group |
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