CN111349240B - Modified polyphenylene sulfide with high glass transition temperature and preparation method thereof - Google Patents
Modified polyphenylene sulfide with high glass transition temperature and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a modified polyphenylene sulfide with high glass transition temperature and a preparation method thereof, wherein the preparation method comprises the following steps: under the action of a catalyst, atomic oxygen in ozone is grafted on sulfur atoms of the polyphenylene sulfide through electron irradiation to prepare the modified polyphenylene sulfide with high glass transition temperature. The prepared modified polyphenylene sulfide with high glass transition temperature is polyphenylene sulfide with each sulfur atom randomly connected with N oxygen atoms, wherein random means that N corresponding to all sulfur atoms is a random number in an interval [0,2], the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.50-1.77, and the glass transition temperature of the modified polyphenylene sulfide with high glass transition temperature is more than or equal to 410 ℃. The preparation method has the advantages of simple process, mild reaction conditions and low cost; the prepared product has high glass transition temperature, excellent acid resistance and good application prospect.
Description
Technical Field
The invention belongs to the technical field of high-performance high polymer materials, relates to modified polyphenylene sulfide with high glass transition temperature and a preparation method thereof, and particularly relates to a method for obtaining the modified polyphenylene sulfide with high glass transition temperature by grafting oxygen atoms with a certain molar ratio on the polyphenylene sulfide and a product prepared by the method.
Background
Polyphenylene sulfide is a thermoplastic resin having a thiophenyl group in a molecular main chain, and is entirely called as polyphenylene sulfide. Polyphenylene sulfide is a crystalline polymer with the glass transition temperature of 150 ℃, is used as a structural high polymer material due to excellent corrosion resistance, radiation resistance and flame retardant property and balanced physical and mechanical properties, is widely applied to the fields of electronic and electric appliances, aerospace, automobile transportation and the like, and is a special engineering plastic with excellent comprehensive performance.
Although the comprehensive performance of polyphenylene sulfide is excellent and the heat resistance of polyphenylene sulfide is stronger than that of common plastics, with the wide application of polyphenylene sulfide in various industries, the application of polyphenylene sulfide in H-grade and C-grade electrical materials, cement kiln tail high-temperature filter materials above 250 ℃, high-temperature printing transmission belts above 280 ℃ and molding structural member materials above 300 ℃ is greatly limited due to the vitrification temperature of polyphenylene sulfide of 150 ℃. Chemical modification is a method of changing the physicochemical properties of a polymer through a chemical reaction, and is also a modification method which is commonly used for polymers. In order to improve the heat resistance of polyphenylene sulfide, polyphenylene sulfide sulfone is prepared by oxidizing polyphenylene sulfide with peroxyacetic acid in the prior art, and although the heat resistance is improved to a certain extent, the process control is difficult, the oxidation grafting rate is difficult to control, and in addition, the reaction time is long, the cost is high, and the industrialization is difficult.
Therefore, the development of the preparation method of the modified polyphenylene sulfide with simple process and high glass transition temperature has great practical significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of modified polyphenylene sulfide with simple process and high glass transition temperature. According to the invention, oxygen atoms are grafted on sulfur atoms of polyphenylene sulfide through electron irradiation, so that each sulfur atom is randomly connected with 0-2 oxygen atoms, the glass transition temperature of the polyphenylene sulfide is increased, and the glass transition temperature of the finally prepared modified polyphenylene sulfide reaches above 410 ℃.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the modified polyphenylene sulfide with high glass transition temperature grafts the atomic oxygen in the ozone on the sulfur atom of the polyphenylene sulfide by electron irradiation under the action of a catalyst.
The invention selects the electron irradiation method as the modification method, has short reaction time and can accurately and quickly provide energy; meanwhile, ozone is selected as an oxygen atom raw material, the oxidation activity of the ozone is high, the oxidation grafting rate can be controlled accurately by adjusting the flow of the ozone, and the oxygen atoms are grafted on the polyphenylene sulfide, so that the electron cloud density of a benzene ring is reduced by the conjugation effect formed by sulfur-oxygen bonds, and the vitrification temperature is obviously increased. In addition, the grafting oxidation process of the invention does not influence the excellent acid resistance of the polyphenylene sulfide.
As a preferable technical scheme:
the preparation method of the modified polyphenylene sulfide with the high glass transition temperature comprises the following specific steps:
(1) Dipping polyphenylene sulfide into an aqueous solution of a catalyst;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by using a high-energy electron beam with energy of 0.1-10 Mev for grafting reaction until the weight of the system is increased by 22-26 wt%; under the action of a catalyst, through high-energy electron radiation, a part of oxygen atoms provided by ozone react with polyphenylene sulfide to graft oxygen atoms on the sulfur atoms in the molecules of the polyphenylene sulfide, the form of grafting the oxygen atoms on the polyphenylene sulfide is a random order state, the energy of a high-energy electron beam can be adjusted within a proper range, but the energy is not too high, and the intensity of the polyphenylene sulfide can be influenced due to the excessive energy of the high-energy electron beam; the energy of the high-energy electron beam is too small, so that oxygen atoms are difficult to be grafted on sulfur atoms of polyphenylene sulfide sufficiently, and the glass transition temperature is not obviously improved;
(3) And taking out the reaction product, and washing and drying to obtain the modified polyphenylene sulfide with high glass transition temperature.
The preparation method of the modified polyphenylene sulfide with high glass transition temperature is characterized in that the polyphenylene sulfide is in the form of fiber, film, powder, mould or particle. The form of polyphenylene sulfide is not limited to this, and only some of the possible forms of polyphenylene sulfide are exemplified here. The modified polyphenylene sulfide with various forms can be prepared by the preparation method, which greatly enriches the form types of high-temperature organic materials.
In the preparation method of the modified polyphenylene sulfide with high glass transition temperature, the concentration of the aqueous solution of the catalyst is 0.1-0.5 wt%. The concentration of the aqueous solution of the catalyst can be adjusted within a certain range by a person skilled in the art, but the adjustment range is not too large, and the concentration is too large, so that the waste of the catalyst is caused, and the cost is increased; if the concentration is too low, it is difficult to graft oxygen atoms to sulfur atoms of polyphenylene sulfide sufficiently, and the glass transition temperature is not remarkably increased.
In the preparation method of the modified polyphenylene sulfide with high glass transition temperature, the catalyst is potassium permanganate or sodium perborate.
In the preparation method of the modified polyphenylene sulfide with high glass transition temperature, the mass ratio of the adding amount of the polyphenylene sulfide to the adding amount of the catalyst in the system in the step (1) is 100-200. The mass ratio can be adjusted within a certain range by a person skilled in the art, but the adjustment range is not too large, the mass ratio is too large, oxygen atoms are difficult to be grafted on sulfur atoms of polyphenylene sulfide sufficiently, and the glass transition temperature is not obviously increased; the mass ratio is too small, i.e. the adding amount of the catalyst is too much, so that the waste of the catalyst is caused, and the cost is increased.
According to the preparation method of the modified polyphenylene sulfide with the high glass transition temperature, the flow rate of the ozone is Mg/min, and M is 1-2 times of the mass of the polyphenylene sulfide in the step (1). The invention can accurately control the oxidation grafting rate by controlling the flow of ozone, thereby controlling the performance of the product. The ozone flow can be adjusted within a proper range, but the intensity of the polyphenylene sulfide can be influenced by overlarge ozone flow; the flow rate of ozone is too small, the grafting of oxygen atoms is insufficient, and the increase of the glass transition temperature is not obvious.
The invention also provides the modified polyphenylene sulfide with high glass transition temperature prepared by the preparation method, wherein each sulfur atom is randomly connected with N oxygen atoms, N corresponding to all the sulfur atoms is a random number in an interval [0,2], the random number is a clear mathematical concept, namely the number of the oxygen atoms connected with the sulfur atoms in the polyphenylene sulfide is 0, 1 or 2, at least one sulfur atom is connected with 0 oxygen atom, at least one sulfur atom is connected with 2 oxygen atoms, the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.50-1.77, and the glass transition temperature of the modified polyphenylene sulfide with high glass transition temperature is more than or equal to 410 ℃. The molar ratio of oxygen atoms to sulfur atoms can be adjusted within a certain range by a person skilled in the art, but the adjustment range is not too large, and the strength of the polyphenylene sulfide is affected by too large molar ratio; the molar ratio is too small, the oxygen atom grafting is insufficient, and the glass transition temperature is not obviously improved. The above molar ratio is a molar ratio range which is obtained by the research of the invention and has obvious improvement on the glass transition temperature.
As a preferred technical scheme:
the LOI of the modified polyphenylene sulfide with high glass transition temperature is more than or equal to 32 percent, and no molten drop is generated during combustion. The performance parameters of the modified polyphenylene sulfide prepared by the present invention are not limited thereto, and only some of the performance parameters of the modified polyphenylene sulfide prepared by the present invention are listed here. The invention overcomes the defect of molten drop generation during combustion by modifying the polyphenylene sulfide, and obviously improves the flame retardant property of the polyphenylene sulfide.
In the modified polyphenylene sulfide with the high glass transition temperature, the tensile strength retention rate of the modified polyphenylene sulfide fiber or the film with the high glass transition temperature is not less than 96% after the modified polyphenylene sulfide fiber or the film with the high glass transition temperature is soaked in a solution with the temperature of 80 ℃ and the pH value of = 1-3 for 2 hours, and the modified polyphenylene sulfide with the high glass transition temperature has excellent acid resistance.
The invention mechanism is as follows:
according to the invention, an electron irradiation method is selected as a modification method, ozone is used as an oxygen atom raw material to modify the polyphenylene sulfide, the electron irradiation method has short reaction time and can accurately and quickly provide energy, the oxidation activity of the ozone is high, and the oxidation grafting rate can be accurately controlled by adjusting the flow of the ozone. The method has the advantages of simple process control, simple control of the oxidation grafting rate, short reaction time and low cost, and overcomes the defects of difficult process control, difficult control of the oxidation grafting rate, long reaction time, high cost and difficult industrialization of the conventional polyphenylene sulfide oxidation modification technology. In addition, the grafting oxidation process of the invention does not influence the excellent acid resistance of the polyphenylene sulfide.
Has the beneficial effects that:
(1) The preparation method of the modified polyphenylene sulfide with high glass transition temperature has the advantages of simple process, mild reaction conditions and low cost;
(2) The modified polyphenylene sulfide with high glass transition temperature has the characteristics of high glass transition temperature, excellent acid resistance, no molten drop during combustion, low thermal shrinkage at high temperature and the like, greatly expands the application range of polyphenylene sulfide, enriches the application of the polyphenylene sulfide in high-temperature organic materials, and has good application prospect.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
A preparation method of modified polyphenylene sulfide with high glass transition temperature comprises the following steps:
(1) Dipping 10g of polyphenylene sulfide fiber with the fineness of 1.5 deniers and the length of 6 millimeters in 100g of 0.1wt% potassium permanganate aqueous solution;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by using a high-energy electron beam with energy of 0.1Mev to perform grafting reaction until the weight of the system is increased by 22wt%, wherein the flow rate of the ozone is 10g/min;
(3) And taking out the reaction product, washing and drying to obtain the modified polyphenylene sulfide fiber with high glass transition temperature.
The prepared modified polyphenylene sulfide fiber with high glass transition temperature has the tensile strength retention rate of 96 percent after being soaked in a solution with the temperature of 80 ℃ and the pH value of 1 for 2 hours, the glass transition temperature of 410 ℃ and the LOI of 33 percent, and no molten drop is generated during combustion. The molar ratio of oxygen atoms to sulfur atoms in the modified polyphenylene sulfide is 1.50.
Example 2
A preparation method of modified polyphenylene sulfide with high glass transition temperature comprises the following steps:
(1) Dipping 50 g of polyphenylene sulfide film into 100g of 0.5wt% sodium perborate aqueous solution;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by adopting a high-energy electron beam with energy of 10Mev to carry out grafting reaction until the weight of the system is increased by 26wt%, wherein the flow rate of the ozone is 100g/min.
(3) And taking out the reaction product, washing and drying to obtain the modified polyphenylene sulfide film with high glass transition temperature.
The tensile strength retention rate of the prepared modified polyphenylene sulfide film with the high glass transition temperature is 98 percent after the film is soaked in a solution with the temperature of 80 ℃ and the pH value of 2 for 2 hours, the glass transition temperature of the film is 430 ℃, the LOI of the film is 39 percent, and no molten drop is generated during combustion. In the modified polyphenylene sulfide molecule, each sulfur atom is randomly connected with N oxygen atoms, wherein N corresponding to all sulfur atoms is a random number in an interval [0,2], and the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.77.
Example 3
A preparation method of modified polyphenylene sulfide with high glass transition temperature comprises the following steps:
(1) Dipping 45 g of polyphenylene sulfide powder into 100g of 0.3wt% sodium perborate aqueous solution;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by adopting a high-energy electron beam with energy of 5Mev to carry out grafting reaction until the weight of the system is increased by 24wt%, wherein the flow rate of the ozone is 67.5g/min.
(3) And taking out the reaction product, and washing and drying to obtain the modified polyphenylene sulfide powder with high glass transition temperature.
The prepared modified polyphenylene sulfide powder with high glass transition temperature has the glass transition temperature of 425 ℃, the LOI of 35 percent and no molten drop generation during combustion. In the modified polyphenylene sulfide molecule, each sulfur atom is randomly connected with N oxygen atoms, wherein random refers to that N corresponding to all sulfur atoms is a random number in an interval [0,2], and the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.64.
Example 4
A preparation method of modified polyphenylene sulfide with high glass transition temperature comprises the following steps:
(1) Dipping 24 g of polyphenylene sulfide mold in 100g of 0.2wt% sodium perborate aqueous solution;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by adopting a high-energy electron beam with energy of 3Mev to carry out grafting reaction until the weight of the system is increased by 23wt%, wherein the flow rate of the ozone is 28.8g/min;
(3) And taking out the reaction product, washing and drying to obtain the modified polyphenylene sulfide mold with high glass transition temperature.
The prepared modified polyphenylene sulfide mold with high glass transition temperature has the glass transition temperature of 415 ℃, the LOI of 34 percent and no molten drop generation during combustion. In the modified polyphenylene sulfide molecule, each sulfur atom is randomly connected with N oxygen atoms, wherein N corresponding to all sulfur atoms is a random number in an interval [0,2], and the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.57.
Example 5
A preparation method of modified polyphenylene sulfide with high glass transition temperature comprises the following steps:
(1) Dipping 60 g of polyphenylene sulfide particles into 100g of 0.4wt% potassium permanganate aqueous solution;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by using a high-energy electron beam with energy of 8Mev to perform grafting reaction until the weight of the system is increased by 25wt%, wherein the flow rate of the ozone is 108 g/min;
(3) And taking out the reaction product, washing and drying to obtain the modified polyphenylene sulfide particles with high glass transition temperature.
The prepared modified polyphenylene sulfide particles with high glass transition temperature have the glass transition temperature of 428 ℃, the LOI of 37 percent and no molten drop generation during combustion. In the modified polyphenylene sulfide molecule, each sulfur atom is randomly connected with N oxygen atoms, wherein N corresponding to all sulfur atoms is a random number in an interval [0,2], and the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.70.
Example 6
A preparation method of modified polyphenylene sulfide with high glass transition temperature comprises the following steps:
(1) Dipping 40 g of polyphenylene sulfide fiber with the fineness of 2.0 denier and the length of 51 mm in 100g of 0.2wt% potassium permanganate aqueous solution;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by adopting a high-energy electron beam with energy of 6Mev to carry out grafting reaction until the weight of the system is increased by 23wt%, wherein the flow rate of the ozone is 48g/min;
(3) And taking out the reaction product, and washing and drying to obtain the modified polyphenylene sulfide fiber with high glass transition temperature.
The prepared modified polyphenylene sulfide fiber with high glass transition temperature has the tensile strength retention rate of 99 percent after being soaked in a solution with the temperature of 80 ℃ and the pH value of 3 for 2 hours, the glass transition temperature of 422 ℃ and the LOI of 32 percent, and no molten drop is generated during combustion. In the modified polyphenylene sulfide molecule, each sulfur atom is randomly connected with N oxygen atoms, wherein the random refers to that N corresponding to all the sulfur atoms is a random number in an interval [0,2], and the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.57.
Claims (9)
1. The preparation method of the modified polyphenylene sulfide with high glass transition temperature is characterized by comprising the following specific steps:
(1) Dipping polyphenylene sulfide into an aqueous solution of a catalyst;
(2) Continuously introducing ozone into the system in the step (1), fully mixing, and simultaneously irradiating the system in the step (1) by using a high-energy electron beam with energy of 0.1-10 Mev for grafting reaction until the weight of the system is increased by 22-26 wt%;
(3) Taking out the reaction product, and washing and drying the reaction product;
the modified polyphenylene sulfide is a polyphenylene sulfide in which each sulfur atom is randomly connected with N oxygen atoms, wherein N corresponding to all the sulfur atoms is a random number in an interval [0,2], the molar ratio of the oxygen atoms to the sulfur atoms in the modified polyphenylene sulfide is 1.50-1.77, and the glass transition temperature of the modified polyphenylene sulfide with high glass transition temperature is more than or equal to 410 ℃.
2. The method as set forth in claim 1, wherein the polyphenylene sulfide is in the form of fiber, film, powder, mold or pellet.
3. The method of claim 1, wherein the concentration of the aqueous solution of the catalyst is 0.1wt% to 0.5wt%.
4. The method for preparing the modified polyphenylene sulfide with high glass transition temperature according to claim 3, wherein the catalyst is potassium permanganate or sodium perborate.
5. The method for preparing modified polyphenylene sulfide with high glass transition temperature according to claim 1, wherein the mass ratio of the addition amount of polyphenylene sulfide to the addition amount of catalyst in the system of step (1) is 100-200.
6. The method for preparing modified polyphenylene sulfide with high glass transition temperature according to claim 1, wherein the flow rate of ozone is Mg/min, and M is 1-2 times of the mass of polyphenylene sulfide in step (1).
7. The modified polyphenylene sulfide having a high glass transition temperature, which is produced by the production process according to any one of claims 1 to 6, characterized in that: the random number refers to a random number in which N corresponding to all sulfur atoms is an interval [0,2], the molar ratio of oxygen atoms to sulfur atoms in the modified polyphenylene sulfide is 1.50-1.77, and the glass transition temperature of the modified polyphenylene sulfide with high glass transition temperature is more than or equal to 410 ℃.
8. The high glass transition temperature modified polyphenylene sulfide of claim 7, wherein the LOI of the high glass transition temperature modified polyphenylene sulfide is 32% or more and no molten drop is generated when it is burned.
9. The modified polyphenylene sulfide with high glass transition temperature as claimed in claim 8, wherein the tensile strength retention of the modified polyphenylene sulfide fiber or film with high glass transition temperature is not less than 96% after soaking in a solution with a temperature of 80 ℃ and a pH value = 1-3 for 2 hours.
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| JP3230258B2 (en) * | 1991-11-18 | 2001-11-19 | 東ソー株式会社 | Curing method of polyphenylene sulfide |
| CN100567371C (en) * | 2004-07-23 | 2009-12-09 | 东丽株式会社 | Polyarylene sulfide oxide, solid article and manufacture method thereof |
| US8895667B2 (en) * | 2009-07-17 | 2014-11-25 | Tyco Electronics Corporation | Methods of making reversible crosslinked polymers and related methods |
| CN104292462A (en) * | 2014-09-17 | 2015-01-21 | 黄孟良 | Polyphenylene sulfide/polyphenylene sulfide sulphone copolymer and preparation method thereof |
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|---|---|---|---|---|
| CN1133857A (en) * | 1994-12-14 | 1996-10-23 | 赫彻斯特股份公司 | Process for surface oxidation of polyarylene thioethers |
| CN105113209A (en) * | 2015-09-29 | 2015-12-02 | 苏州金泉新材料股份有限公司 | Preparation method of PPS fibers with self-extinguishment and free of molten drops |
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