CN116333279A

CN116333279A - Polycarbonate toughening resin

Info

Publication number: CN116333279A
Application number: CN202310613711.5A
Authority: CN
Inventors: 李洪国; 魏怀建; 李宜格; 王波; 傅海
Original assignee: Shandong Lianxin Environmental Protection Technology Co ltd
Current assignee: Shandong Lianxin Environmental Protection Technology Co ltd
Priority date: 2023-05-29
Filing date: 2023-05-29
Publication date: 2023-06-27
Anticipated expiration: 2043-05-29
Also published as: CN116333279B

Abstract

A polycarbonate toughening resin belongs to the technical field of toughening resins. The method is characterized in that: the components are terpolymers of ethylene oxide, phthalic anhydride and carbon dioxide. The ethylene oxide-phthalic anhydride-carbon dioxide terpolymer is named as ethylene phthalate-ethylene carbonate copolymer, abbreviated PECP. After phthalic anhydride is introduced into the copolymer, the molecular structure of the copolymer shows a tiling effect, and the molecules are easy to form a layered structure because of the tiling effect, so that the barrier property of the copolymer is greatly improved. The ethylene oxide introduced is a flexible monomer capable of increasing the toughness of the copolymer. The synthetic PECP is a high-toughness barrier material without the influence of other monomers, and can be used as a toughening agent of the PPCP.

Description

Polycarbonate toughening resin

Technical Field

The invention belongs to the technical field of toughening resins, and particularly relates to a polycarbonate toughening resin with good barrier property.

Background

Propylene phthalate-propylene carbonateThe alkene ester copolymer (PPCP) is a biodegradable barrier material, and the water vapor permeability coefficient (23 ℃) can reach 0.1 g.mm/(m) ² 24 h) or less, and the oxygen permeability coefficient (23 ℃) can reach 0.2cm ³ ·mm/（m ² 24 h.0.1 MPa) or less, but PPCP has high strength and low toughness. In the case of film products or barrier layer materials, a large amount of toughening agents such as poly (adipic acid)/butylene terephthalate (PBAT) are required to be added for toughening. The barrier property of the materials used for toughening is far lower than that of PPCP, and the barrier property of the materials can be influenced after the materials are blended with the PPCP. Therefore, there is an urgent need to develop a toughening agent suitable for PPCP and capable of maintaining its high barrier properties.

Disclosure of Invention

The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides the polycarbonate toughening resin with high barrier property.

The technical scheme adopted for solving the technical problems is as follows: the polycarbonate toughening resin is characterized in that: the components are terpolymers of ethylene oxide, phthalic anhydride and carbon dioxide.

The ethylene oxide-phthalic anhydride-carbon dioxide terpolymer is named as ethylene phthalate-ethylene carbonate copolymer, abbreviated PECP. After phthalic anhydride is introduced into the copolymer, the molecular structure of the copolymer shows a tiling effect, and the molecules are easy to form a layered structure because of the tiling effect, so that the barrier property of the copolymer is greatly improved. The ethylene oxide introduced is a flexible monomer capable of increasing the toughness of the copolymer. The synthetic PECP is a high-toughness barrier material, can be used as a toughening agent of the PPCP, is more uniformly mixed with the PPCP, has obvious toughening effect, and can well maintain the barrier property of the blending material.

Preferably, in the polycarbonate-based toughening resin, the terpolymer has a number average molecular weight of 1000g/mol to 2.5X10 ⁵ g/mol. PECP with different molecular weights can be used as a toughening agent in different products, and when PECP with the molecular weight is preferably used as the toughening agent, the toughening effect is better and the toughening effect can be betterEnhancing the barrier properties of the material.

Preferably, in the polycarbonate toughening resin, the structural unit of the terpolymer comprises a polyester segment, a polycarbonate segment and a polyether segment, wherein the molar ratio of the polyester segment to the polycarbonate segment to the polyether segment is 20-50:45-80:0.05-5; wherein the polyester segment is formed by polymerizing ethylene oxide and phthalic anhydride, the polycarbonate segment is formed by polymerizing ethylene oxide and carbon dioxide, and the polyether segment is formed by self-polymerizing ethylene oxide. The ratio of the polyester segment to the polycarbonate segment is the key to adjusting the combined effect of the PECP toughening effect and the barrier property, and the preferable ratio of the polyester segment to the polycarbonate segment can ensure the properties at the same time.

Preferably, in the above polycarbonate toughening resin, the structural formula of the terpolymer includes formula 1 to formula 3:

1 (1)

Wherein a is more than or equal to 1 and less than or equal to 6000,1, a is more than or equal to 9000,0, c is more than or equal to 600, and a, b and c are integers;

2, 2

Wherein a+c is more than or equal to 1 and less than or equal to 6000,1, b is more than or equal to 9000,0 and d is more than or equal to 600, and a, b, c and d are integers;

3

Wherein a+c is more than or equal to 1 and less than or equal to 9000,1, b is more than or equal to 6000,0 and d is more than or equal to 600, and a, b, c and d are integers.

When the components of the PECP are the preferable structural formula, the PECP is more suitable for being used as a toughening agent of the PPCP, and has excellent toughening effect and barrier property after blending modification.

Preferably, the preparation method of the polycarbonate toughening resin comprises a one-pot one-step method: adding ethylene oxide, phthalic anhydride and a catalyst to a reactor; filling carbon dioxide to a reaction pressure of 1-2 MPa, heating to a reaction temperature of 25-80 ℃ and stirring for reaction to prepare a glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate.

Preferably, the preparation method of the polycarbonate toughening resin comprises a one-pot multi-step method:

1) Putting ethylene oxide, phthalic anhydride, a catalyst and a solvent into a high-pressure reaction kettle; heating to a reaction temperature of 25-80 ℃ to react until phthalic anhydride is completely reacted;

2) Supplementing ethylene oxide and a catalyst, introducing carbon dioxide to a reaction pressure of 1-2 MPa, keeping the reaction temperature, continuing to react for 3-8 hours, cooling and decompressing;

3) Adding ethylene oxide and phthalic anhydride again, supplementing a catalyst, heating to the reaction temperature for reaction, and stopping the reaction after the monomer reaction is completed to obtain a glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate.

The PECP ternary polymerization can be prepared by the existing one-pot one-step method and one-pot multi-step method.

Preferably, in the one-pot multi-step process, the solvent in step 1) is an excess of ethylene oxide. In the step 1) of the one-pot multi-step method, the excessive ethylene oxide is preferably used as a solvent, the dispersion condition of materials in the solvent is not considered, the process is a polyester segment polymerized based on phthalic anhydride, the molecular contact rate is greatly improved in the ethylene oxide environment, and the copolymerization efficiency is higher. And the subsequent desolventizing process can be reduced, and the energy consumption is reduced.

The excessive ethylene oxide refers to that the molar ratio of the amount of the ethylene oxide added as a solvent to the ethylene oxide as a comonomer is 3-10:1 when the materials are added. At this time, the molar ratio of the polyester segment to the polycarbonate segment can be ensured, and the proper copolymerization reaction rate can be ensured.

Preferably, in the one-pot one-step method and the one-pot multi-step method, the molar ratio of the ethylene oxide to the catalyst as the comonomer is 3000:1-100. The molar ratio of the total amount of ethylene oxide to the total amount of phthalic anhydride as the comonomer is 2-10:1. The preferred material ratios are effective to control the molar ratio of polyester segments to polycarbonate segments in the copolymer to yield the copolymer in the preferred ratios described above.

Specifically, in the one-pot multi-step method, the solvent in the step 1) is one of 2-methyltetrahydrofuran, tetrahydrofuran or n-butyl ether. The solvent can keep the smooth polymerization of the polyester segment.

Preferably, in the one-pot one-step method and the one-pot multi-step method, the reaction temperature is 30-38 ℃. The ethylene oxide monomer is more suitable for polymerization under the condition of lower temperature, the molecular weight distribution of the obtained product is uniform, the molecular weight is easy to control, the self-polymers generated by the self-polymerization of the monomers are fewer, and the content of components meeting the structural formulas of formulas 1-3 in the copolymer is higher, so that the ethylene oxide monomer is more suitable for dispersion and compatibility in PPCP, and therefore, the ethylene oxide monomer plays a better role in toughening the PPCP. The reaction pressure is 1.1-1.3 MPa. The preferred reaction pressure, in combination with the preferred reaction temperature, allows for better control of the rate at which carbon dioxide participates in the copolymerization, thereby allowing for higher levels of copolymer to be polymerized to the preferred structural unit molar ratios described above.

Specifically, the catalyst comprises a zinc-based catalyst system, a metalloporphyrin-based catalyst system, a beta-diimine metal complex catalyst, a double metal cyanide complex catalyst, a SalenMX catalyst system, a rare earth catalyst system, a multi-metal catalyst system and a Lewis acid/alkali pair.

The Lewis acid/alkali pair is used as a catalyst, so that higher catalytic efficiency can be maintained, and metal impurities can not be introduced. More specifically, the lewis acid includes one or more of triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tris (pentafluorophenyl) boron, diethylmethoxyborane, bis (trimethylphenyl) boron fluoride, trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, tris (pentafluorophenyl) aluminum. The Lewis base comprises one or more of tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide, tetra-n-propyl ammonium iodide, bis (triphenylphosphine) ammonium chloride, tetrabutylphosphine bromide, triethylene diamine, diethylene triamine, triethylene tetramine, triethylamine, tri-n-propylamine and tetra-n-butylamine.

Compared with the prior art, the polycarbonate toughening resin has the following beneficial effects: the invention provides an ethylene oxide-phthalic anhydride-carbon dioxide terpolymer. After phthalic anhydride is introduced into the copolymer, the molecular structure of the copolymer shows a tiling effect, and the molecules are easy to form a layered structure because of the tiling effect, so that the barrier property of the copolymer is greatly improved. The ethylene oxide introduced is a flexible monomer capable of increasing the toughness of the copolymer. The synthetic PECP is a high-toughness barrier material, can be used as a toughening agent of the PPCP, is more uniformly mixed with the PPCP, has obvious toughening effect, and can well maintain the barrier property of the blending material.

Detailed Description

The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.

Example 1

In a dry kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, ethylene oxide, phthalic anhydride and a catalyst are added into a reactor, and the mol ratio of the ethylene oxide to the catalyst is 3000:2; the molar ratio of ethylene oxide to phthalic anhydride is 3.5:1, and the catalyst is a complex of trimethylaluminum and tetra-n-butyl ammonium chloride according to the molar ratio of 2:1; filling carbon dioxide to 1.2MPa, heating to 35 ℃ and stirring for reaction to prepare glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate. The molar ratio of the polyester segment, the polycarbonate segment and the polyether segment in the obtained terpolymer was 30:62:1.3, and the proportion of the components satisfying the structural formulas 1 to 3 in the copolymer was 95.3%.

Example 2

In the dry kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, ethylene oxide, phthalic anhydride and a catalyst are added into a reactor, and the mol ratio of the ethylene oxide to the catalyst is 3000:3; the molar ratio of ethylene oxide to phthalic anhydride is 2.5:1, and the catalyst is a complex of tributyl boron and tetra-n-butyl ammonium bromide according to the molar ratio of 4:1; filling carbon dioxide to 1.3MPa, heating to 38 ℃ and stirring for reaction to prepare glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate. The molar ratio of the polyester segment, the polycarbonate segment and the polyether segment in the obtained terpolymer was 40:48:0.6, and the proportion of the components satisfying the structural formulas 1 to 3 in the copolymer was 94.7%.

Example 3

In a dry kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, ethylene oxide, phthalic anhydride and a catalyst are added into a reactor, and the mol ratio of the ethylene oxide to the catalyst is 3000:1.5; the molar ratio of ethylene oxide to phthalic anhydride is 4.5:1, and the catalyst is a complex of triisobutylaluminum and tetra-n-propyl ammonium chloride according to the molar ratio of 3:1; filling carbon dioxide to 1.1MPa, heating to 30 ℃ and stirring for reaction to prepare glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate. The molar ratio of the polyester segment, the polycarbonate segment and the polyether segment in the obtained terpolymer was 23:76:2.4, and the proportion of the components satisfying the structural formulas 1 to 3 in the copolymer was 93.9%.

Example 4

1) In a dry kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, and part of ethylene oxide, phthalic anhydride, catalyst and ethylene oxide serving as a solvent are fed into a high-pressure reaction kettle; the molar ratio of ethylene oxide as comonomer to catalyst in this step was 3000:10, the molar ratio of ethylene oxide as comonomer to phthalic anhydride was 3:1, the molar ratio of the amount of ethylene oxide as solvent to ethylene oxide as comonomer was 4.5:1; heating to 35 ℃ to react until phthalic anhydride is completely reacted; the catalyst is a complex of triethylboron and tetra-n-butyl ammonium chloride according to a molar ratio of 1.5:1.

2) And supplementing triethylboron to the system, wherein the mol ratio of triethylboron to tetra-n-butyl ammonium chloride is 2.5:1, introducing carbon dioxide to 1.2MPa, maintaining the reaction temperature, continuing to react for 3 hours, cooling and decompressing.

3) Adding 1/2 of phthalic anhydride in the molar quantity in the step 1) again, supplementing triethylboron to the molar ratio of triethylboron to tetra-n-butyl ammonium chloride in the system of 3:1, heating to the reaction temperature, and stopping the reaction after the reaction is completed to obtain a glue solution; and washing and devolatilizing the glue solution to obtain polycarbonate, wherein the molar ratio of the polyester segment to the polycarbonate segment to the polyether segment in the obtained terpolymer is 22:68:4.6, and the proportion of the components with the structural formula satisfying the formulas 1-3 in the copolymer is 91.2%.

Example 5

1) In a dry kettle, replacing air in the kettle with high-purity carbon dioxide, starting to feed, and feeding ethylene oxide, phthalic anhydride, a catalyst and 2-methyltetrahydrofuran into a high-pressure reaction kettle; the molar ratio of ethylene oxide to catalyst is 3000:6; the molar ratio of ethylene oxide to phthalic anhydride is 1.2:1; the molar ratio of the 2-methyltetrahydrofuran to the ethylene oxide is 3:1; the reaction is carried out at the reaction temperature of 30 ℃ until the phthalic anhydride is completely reacted; the catalyst is a complex of triisobutylaluminum and tetra-n-butylammonium bromide according to a molar ratio of 1:1.

2) And 2.6 times of ethylene oxide with the molar quantity of the step 1) is supplemented, triisobutylaluminum is supplemented to the molar ratio of triisobutylaluminum to tetra-n-butylammonium bromide in the system of 2:1, and carbon dioxide is introduced to the reaction pressure of 1.1MPa, so that the reaction temperature is kept for continuous reaction for 8 hours.

3) Adding the same amount of ethylene oxide and phthalic anhydride as in the step 1) again, and stopping the reaction after the monomer reaction is completed from triisobutylaluminum to the mole ratio of triisobutylaluminum to tetra-n-butylammonium bromide in the system of 3:1 to obtain a glue solution; and washing and devolatilizing the glue solution to obtain polycarbonate, wherein the mole ratio of the polyester segment to the polycarbonate segment to the polyether segment in the obtained terpolymer is 43:47:0.3, and the proportion of the components with the structural formula satisfying the formulas 1-3 in the copolymer is 93.7%.

Example 6

1) In a dry kettle, replacing air in the kettle with high-purity carbon dioxide, starting to feed, and feeding ethylene oxide, phthalic anhydride, a catalyst and n-butyl ether into a high-pressure reaction kettle; the molar ratio of ethylene oxide to catalyst was 3000:4; the molar ratio of ethylene oxide to phthalic anhydride is 1.5:1; the molar ratio of the n-butyl ether to the ethylene oxide is 10:1; the reaction is carried out at the reaction temperature of 38 ℃ until the phthalic anhydride is completely reacted; the catalyst is a complex of tributyl boron and triethylene diamine according to a molar ratio of 2:1.

2) 2.8 times of ethylene oxide is added in the molar quantity of the step 1), tributyl boron is added to the molar ratio of tributyl boron to triethylenediamine in the system of 2.5:1, carbon dioxide is introduced to the reaction pressure of 1.2MPa, and the reaction temperature is kept for continuous reaction for 6 hours.

3) Adding 2/3 of ethylene oxide and phthalic anhydride in the step 1) again, supplementing tributyl boron to the mole ratio of tributyl boron to triethylenediamine in the system of 3:1, heating to the reaction temperature for reaction, and stopping the reaction after the monomer reaction is completed to obtain a glue solution; and washing and devolatilizing the glue solution to obtain polycarbonate, wherein the molar ratio of the polyester segment to the polycarbonate segment to the polyether segment in the obtained terpolymer is 48:51:1.3, and the proportion of the components with the structural formula satisfying the formulas 1-3 in the copolymer is 93.1%.

Example 7

Adding ethylene oxide, phthalic anhydride and a catalyst into a reactor, wherein the mol ratio of the ethylene oxide to the catalyst is 3000:100; the molar ratio of the ethylene oxide to the phthalic anhydride is 10:1, and the catalyst is a diethyl zinc-glycerin ternary system; filling carbon dioxide to 2MPa, heating to 80 ℃ and stirring for reaction to prepare glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate. The molar ratio of the polyester segment, the polycarbonate segment and the polyether segment in the obtained terpolymer was 20:80:5, and the proportion of the components satisfying the structural formulas 1 to 3 in the copolymer was 84.7%.

Example 8

Adding ethylene oxide, phthalic anhydride and a catalyst into a reactor, wherein the mol ratio of the ethylene oxide to the catalyst is 3000:1; the molar ratio of the ethylene oxide to the phthalic anhydride is 2:1, and the catalyst is SalenMX-quaternary ammonium salt; filling carbon dioxide to 1MPa, and stirring and reacting at 25 ℃ to prepare glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate. The molar ratio of the polyester segment, the polycarbonate segment and the polyether segment in the obtained terpolymer was 50:45:0.05, and the proportion of the components satisfying the structural formulas 1 to 3 in the copolymer was 87.6%.

Comparative example 1

The equivalent molar amount of ethylene oxide in comparative example 1 was replaced with propylene oxide and the reaction temperature was increased to 50 ℃ without changing the other conditions to obtain the PPCP finished product.

5. Performance test:

1) Molecular weight: the molecular weight of the polymer was analyzed by GPC, see method "GB/T31124-2014 appendix B".

2) Tensile properties: according to GB/T1040.1 and GB/T1040.2.

3) Water vapor transmission rate: according to GB/T1037.

4) Oxygen transmission rate: according to the method of national standard GB/T1038.

The properties of the copolymers prepared in examples 1 to 4 according to the invention and comparative example 1 are shown in Table 1:

table 1 sample performance index table

It follows that the barrier properties of ethylene phthalate-ethylene carbonate copolymer (PECP) are comparable to those of propylene phthalate-propylene carbonate copolymer (PPCP), but the toughness is much higher than PPCP, and can be used as a toughening agent for improving the toughness of PPCP.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A polycarbonate toughening resin is characterized in that: the components are terpolymers of ethylene oxide, phthalic anhydride and carbon dioxide.

2. The polycarbonate-based toughening resin according to claim 1, wherein: the number average molecular weight of the terpolymer is 1000 g/mol-2.5X10 ⁵ g/mol。

3. The polycarbonate-based toughening resin according to claim 1, wherein: the structural unit of the terpolymer comprises a polyester segment, a polycarbonate segment and a polyether segment, wherein the molar ratio of the polyester segment to the polycarbonate segment to the polyether segment is 20-50:45-80:0.05-5; wherein the polyester segment is formed by polymerizing ethylene oxide and phthalic anhydride, the polycarbonate segment is formed by polymerizing ethylene oxide and carbon dioxide, and the polyether segment is formed by self-polymerizing ethylene oxide.

4. A polycarbonate-based toughening resin according to claim 1 or 3, wherein the structural formula of the terpolymer comprises formula 1 to formula 3:

1 (1)

Wherein a is more than or equal to 1 and less than or equal to 6000,1, a is more than or equal to 9000,0 and c is more than or equal to 600, and a, b and c are integers;

2, 2

3

5. The polycarbonate-based toughening resin according to claim 1, wherein the preparation method comprises the following steps: adding ethylene oxide, phthalic anhydride and a catalyst to a reactor; filling carbon dioxide to a reaction pressure of 1-2 MPa, heating to a reaction temperature of 25-80 ℃ and stirring for reaction to prepare a glue solution; and washing and devolatilizing the glue solution to obtain the polycarbonate.

6. The polycarbonate-based toughening resin according to claim 1, wherein the preparation method comprises the following steps:

7. The toughened polycarbonate resin as described in claim 6, wherein said solvent in step 1) is an excess of ethylene oxide.

8. The method for preparing a polycarbonate toughening resin according to claim 6, wherein the solvent is one of 2-methyltetrahydrofuran, tetrahydrofuran or n-butyl ether.

9. The polycarbonate-based toughening resin according to claim 5 or 6, wherein the reaction temperature is 30-38 ℃.

10. The polycarbonate-based toughening resin according to claim 5 or 6, wherein the reaction pressure is 1.1mpa to 1.3mpa.