WO2023104139A1 - Composite polymer material with strong impact resistance and preparation method therefor - Google Patents

Abstract

Disclosed is a composite polymer material with strong impact resistance. The composite polymer material is prepared from the following raw materials in parts by weight: 1-9 parts of a propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, and 0.05-0.2 parts of a compatilizer. By means of the synergistic effect of polycaprolactone having a crystallinity of 45% and the amorphous propylene glycol phthalate-propylene carbonate copolymer, the tensile strength and impact resistance of the composite polymer material are improved. Moreover, by means of adding the auxiliary agents of a talcum powder, titanium dioxide and castor oil, the forming effect of the composite polymer material is improved, and the use safety performance of the material is enhanced; and the material is particularly suitable for product packaging of foods and drugs. In addition, the composite polymer material has good oxygen and water vapor barrier properties, and also has good biodegradability and an excellent environmental protection performance.

Description

Composite polymer material with strong impact resistance and preparation method thereof

This application claims the priority of the Chinese patent application submitted to the China Patent Office on December 08, 2021, with the application number CN202111492887.7, and the title of the invention "a composite polymer material with strong impact resistance and its preparation method", The entire contents of which are incorporated by reference in this application.

technical field

The invention relates to the field of polymer compound compositions, and relates to an IPC classification number C08L (2006.01), in particular to a composite polymer material with strong impact resistance.

Background technique

As plastic polymers are more and more widely used in life, the ensuing environmental problems are becoming more and more serious. Therefore, it is very important to develop and use degradable plastic polymers to replace traditional plastic products. However, due to degradable plastic polymers The raw materials are expensive and the production cost is high, so the resistance to popularization is relatively large. At the same time, the poor compatibility of degradable plastic polymers with other polymers will also lead to a decline in the mechanical properties of the product.

Chinese invention patent CN202010814476.4 discloses a degradable plastic composition, which is produced by blending PLA and PBS. However, PLA is expensive, and it is not easy to popularize and use it in the actual production process. Chinese invention patent CN201210511722.4 discloses a fully degradable bamboo-plastic composite material with ultra-high toughness. The toughness between the plastic matrix is increased by introducing natural plant fibers, but the addition of natural plant fibers will lead to poor molding effect of the material. It is not suitable for the production of blown film process, which limits the preparation of some products.

Contents of the invention

In order to increase the impact resistance of the composite polymer material and improve the use safety of the composite material, the invention provides a composite polymer material with strong impact resistance.

The invention provides a composite polymer material with strong impact resistance. The preparation raw materials include, in parts by weight: 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, and Compatible agent 0.05-0.2 parts.

Preferably, the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide;

The number average molecular weight of the propylene glycol phthalate-propylene carbonate copolymer is 100000-200000 g/mol.

Preferably, the melt flow rate of the polycaprolactone at 160° C. is 5.9-7.9 g/10 min.

Preferably, the polycaprolactone has a number average molecular weight of 80000-100000 g/mol, a water content of 0.3-0.4%, and a crystallinity of 43-48%.

Preferably, the weight ratio of the propylene glycol phthalate-propylene carbonate copolymer to polycaprolactone is (1-7):(4-9).

Preferably, the compatibilizer is selected from one or a combination of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers.

Preferably, the reactive chain extension compatibilizer is selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic acid type compatibilizer, amino type compatibilizer, isocyanate type compatibilizer and oxazoline One or a combination of several types of compatibilizers.

Preferably, in the propylene glycol phthalate-propylene carbonate copolymer, the weight ratio of polycaprolactone to the compatibilizer is 1:(1-4):0.05.

Preferably, the raw materials for preparation also include additives, in parts by weight of 0.1-1 parts.

Preferably, the auxiliary agent is selected from one or a combination of talcum powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene wax and white oil.

Preferably, the auxiliary agent is a combination of talcum powder, titanium dioxide and castor oil.

Preferably, the weight ratio of the talcum powder, titanium dioxide and castor oil is 1:(0.5-1.2):(0.5-0.8).

The present invention also provides a method for preparing a composite polymer material with strong impact resistance described in the above technical solution, comprising the following steps:

(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 50-60°C for 3-5h;

(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 3-10min at 80-120°C;

(3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.

The composite macromolecule material with strong impact resistance provided by the present invention, by adopting the weight ratio of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone (3-5): (5-7), makes composite Polymer materials have good oxygen and water vapor barrier properties, and also have good biodegradability and excellent environmental performance.

Detailed ways

The invention provides a composite polymer material with strong impact resistance. The preparation raw materials include, in parts by weight, 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, 0.05-0.2 parts of compatibilizer.

In the present invention, preferably contain ethylene oxide in the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer, the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is preferably 100000- 200000g/mol.

During the experiment, the applicant found that the molecular weight distribution of the propylene glycol phthalate-propylene carbonate copolymer prepared by adding ethylene oxide is relatively narrow, which is conducive to improving the processing and molding performance of composite polymer materials. Under these conditions, the production cost can also be reduced.

In the present invention, the melt flow rate of the polycaprolactone at 160° C. is preferably 5.9-7.9 g/10 min.

In the present invention, the number average molecular weight of the polycaprolactone is preferably 80000-100000 g/mol, the water content is preferably 0.3-0.4%, and the crystallinity is preferably 43-48%.

In the present invention, the number average molecular weight of the polycaprolactone is preferably 80000-100000 g/mol, the water content is preferably 0.35%, and the crystallinity is preferably 45%.

In the present invention, the weight ratio of the propylene glycol phthalate-propylene carbonate copolymer to polycaprolactone is preferably (1-7): (4-9), more preferably (3-5): (5-7), most preferably 3:7.

The applicant further finds that adopting weight ratio is (3-5): (5-7) the combination of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone can make composite macromolecular polymer It has good water vapor and oxygen barrier properties, which can prevent oxygen from contacting the packaged items to the greatest extent and reduce oxidative deterioration.

In the present invention, the compatibilizer is preferably selected from one or a combination of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers.

In the present invention, the reactive chain extension compatibilizer is preferably selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic type compatibilizer, amino type compatibilizer, isocyanate type compatibilizer and One or more combinations of oxazoline compatibilizers, more preferably one or more combinations selected from epoxy-type compatibilizers, isocyanate-type compatibilizers and oxazoline-type compatibilizers .

In the present invention, in the propylene glycol phthalate-propylene carbonate copolymer, the weight ratio of polycaprolactone to the compatibilizer is preferably 1:(1-4):(0.01-0.05).

In the present invention, the raw materials for preparation preferably include auxiliary agents, and the parts by weight are preferably 0.1-1 parts.

In the present invention, the auxiliary agent is preferably selected from one or more combinations of talcum powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene wax and white oil, More preferred is a combination of talc, titanium dioxide and castor oil. In the present invention, the weight ratio of the talc powder, titanium dioxide and castor oil is preferably 1:(0.5-1.2):(0.5-0.8), more preferably 1:1:0.7.

During the experiment, the applicant found that blending PCL with PPCP with a crystallinity of 45% and adding talcum powder, titanium dioxide and castor oil as additives can make the resulting composite polymer material have good impact resistance and good impact resistance. safety of use. It is speculated that the possible reason is that PCL with a crystallinity of 45% is blended with amorphous PPCP. The molecular chain of PPCP is more flexible and the interaction force between chains is relatively small. The chain segment winds around the ether bond to generate internal rotation, which increases the flexibility of the PCL chain segment and improves the impact resistance of the composite material. And the applicant further found in the experiment that adding talcum powder, titanium dioxide, and castor oil improved the safety of the composite polymer material. It is speculated that the possible reason is that the synergistic effect of titanium dioxide and castor oil can prevent bacteria in the external environment from reaching food. On the surface, reduce the spoilage of food, the fluidity of titanium dioxide in the composite material is not good, the addition of castor oil can promote the movement of titanium dioxide in the composite material, and further increase the use safety effect. The synergistic effect of talc and castor oil can weaken the interfacial resistance between PCL and PPCP, reduce the friction between molecules, improve the compatibility between PCL and PPCP, and further improve the impact resistance.

A second aspect of the present invention provides a method for preparing a composite polymer material with strong impact resistance, comprising the following steps:

(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 50-60°C for 3-5h;

(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 3-10min at 80-120°C;

(3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.

Compared with the prior art, the present invention has the following beneficial effects:

(1) the strong composite macromolecular material of impact resistance of the present invention, by adopting crystallinity is the polycaprolactone of 45% and amorphous propylene glycol phthalate-propylene carbonate copolymer synergistic effect, has improved Tensile strength and impact resistance of composite polymer materials.

(2) The composite polymer material with strong impact resistance of the present invention, by adding talcum powder, titanium dioxide, and castor oil additives, improves the molding effect of the composite polymer material, and improves the use safety performance of the material, and is especially suitable for Product packaging for food, medicine.

(3) The composite polymer material with strong impact resistance of the present invention, by adopting the weight ratio of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone (3-5): (5-7) , so that the composite polymer material has good oxygen and water vapor barrier properties, and also has good biodegradability and excellent environmental performance.

The present invention is specifically described below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, some non-essential improvements made by those skilled in the art according to the content of the present invention above And adjustments still belong to the protection scope of the present invention.

In addition, all raw materials used are commercially available unless otherwise stated.

Example 1

A composite polymer material with strong impact resistance, the preparation raw materials include in parts by weight: 3 parts of propylene glycol phthalate-propylene carbonate copolymer, 7 parts of polycaprolactone, 0.05 parts of compatibilizer, auxiliary agent 0.1 part.

The preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide, and the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is 100000-200000g/mol, purchased from Shandong Lianchuang Industrial Development Group Co., Ltd.

The melt flow rate of the polycaprolactone at 160° C. is 6.9 g/10 min, the number average molecular weight is 80,000 g/mol, the water content is 0.35%, and the crystallinity is 45%. It is purchased from Perstorp, Sweden, and the model is 2200.

Described compatibilizer is epoxy type compatibilizer, purchased from Zhejiang Hangzhou Xusheng New Material Technology Co., Ltd.

The additive is a combination of talcum powder, titanium dioxide and castor oil, with a weight ratio of 1:1:0.7.

A method for preparing a composite polymer material with strong impact resistance, comprising the following steps:

(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 60° C. for 4 hours;

(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 5 minutes at 90°C;

(3) Add the mixture obtained in step (2) into a twin-screw extruder, extrude and granulate at 120° C. to obtain a composite polymer material.

Example 2

A composite polymer material with strong impact resistance. The preparation raw materials include in parts by weight: 3 parts of propylene glycol phthalate-propylene carbonate copolymer, 7 parts of polycaprolactone, 0.15 parts of compatibilizer, auxiliary agent 0.5 servings.

The preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide, and the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is 100000-200000g/mol, purchased from Shandong Lianchuang Industrial Development Group Co., Ltd.

The melt flow rate of the polycaprolactone at 160° C. is 6.9 g/10 min, the number average molecular weight is 80,000 g/mol, the water content is 0.35%, and the crystallinity is 45%. It is purchased from Perstorp, Sweden, and the model is 2200.

The compatibilizer is an oxazoline-type chain extension compatibilizer, purchased from Shanghai Hanluo New Material Co., Ltd.

The additive is a combination of talcum powder, titanium dioxide and castor oil, with a weight ratio of 1:1:0.7.

A method for preparing a composite polymer material with strong impact resistance, comprising the following steps:

(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 60° C. for 4 hours;

(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 5 minutes at 100°C;

(3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 135° C. to obtain a composite polymer material.

Example 3

A composite polymer material with strong impact resistance and a preparation method thereof. The specific steps are the same as those in Example 2, except that the auxiliary agent is a combination of talc powder and titanium dioxide.

Example 4

A composite polymer material with strong impact resistance and a preparation method thereof, the specific steps are the same as in Example 2, the difference is that the melt flow rate of the polycaprolactone at 160°C is 28g/10min, and the number average molecular weight is 50000g/mol.

Example 5

A composite polymer material with strong impact resistance and a preparation method thereof, the specific steps are the same as in Example 2, the difference lies in 6 parts of propylene glycol phthalate-propylene carbonate copolymer, 5 parts of polycaprolactone, compatible 0.2 parts of the agent.

Performance Testing

1. Tensile strength: According to the GB/T1040.3-2006 test standard, the tensile strength of the prepared composite polymer material was tested.

2. Izod unnotched impact strength: according to the GB/T1843-2008 test standard, test the prepared composite polymer material at 23°C for the unnotched Izod impact strength.

3. Biodegradation performance: According to the GB/T19277 test standard, the biodegradation performance of the prepared composite polymer material is tested. The test environment temperature is 58±2°C, the humidity is 50-55%, 60 days after 12 months of forced composting , to observe the degradation state.

The examples were tested according to the above-mentioned standards, and the results are shown in Table 1.

Table 1

the	Tensile strength/MPa	Izod notched impact strength kJ/m 2	biodegradability
Example 1	>35	80.5	Completely degraded
Example 2	>39	82.1	Completely degraded
Example 3	30	74.2	Completely degraded
Example 4	28	72.6	Completely degraded
Example 5	29	73.5	Completely degraded

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (13)

1. A composite polymer material with strong impact resistance is characterized in that the preparation raw materials include in parts by weight: 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, 0.05-0.2 parts of compatibilizer.
2. According to the strong composite polymer material of impact resistance described in claim 1, it is characterized in that, the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide;

   The number average molecular weight of the propylene glycol phthalate-propylene carbonate copolymer is 100000-200000 g/mol.
3. The composite polymer material with strong impact resistance according to claim 1 or 2, characterized in that the melt flow rate of the polycaprolactone at 160°C is 5.9-7.9g/10min.
4. The composite polymer material with strong impact resistance according to claim 1 or 2 is characterized in that the number average molecular weight of the polycaprolactone is 80000-100000g/mol, the water content is 0.3-0.4%, and the crystallinity is 43-48%.
5. The strong composite macromolecular material of impact resistance according to claim 1, is characterized in that, the weight ratio of described propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone is (1-7):( 4-9).
6. The composite polymer material with strong impact resistance according to claim 1, wherein the compatibilizer is selected from one of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers one or a combination of several.
7. According to the composite polymer material with strong impact resistance according to claim 6, it is characterized in that, the reactive chain extension compatibilizer is selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic acid type compatibilizer One or more combinations of compatibilizers, amino-type compatibilizers, isocyanate-type compatibilizers and oxazoline-type compatibilizers.
8. The strong composite macromolecular material of impact resistance according to claim 1, is characterized in that, described propylene glycol phthalate-propylene carbonate copolymer, the weight ratio of polycaprolactone and compatibilizer is 1:( 1-4): 0.05.
9. The composite polymer material with strong impact resistance according to claim 1, characterized in that the preparation raw materials further include additives, the parts by weight are 0.1-1 parts.
10. The composite polymer material with strong impact resistance according to claim 9, wherein the auxiliary agent is selected from talc powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene One or a combination of waxes and white oils.
11. The composite polymer material with strong impact resistance according to claim 10, characterized in that the additive is a combination of talcum powder, titanium dioxide and castor oil.
12. The composite polymer material with strong impact resistance according to claim 11, characterized in that the weight ratio of the talcum powder, titanium dioxide and castor oil is 1:(0.5-1.2):(0.5-0.8).
13. The method for preparing a composite polymer material with strong impact resistance according to any one of claims 9 to 11, characterized in that it comprises the following steps:

    (1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 50-60°C for 3-5h;

    (2) Add the dried propylene phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir at 80-120°C for 3-10min ;

    (3) Add the mixture obtained in step (2) into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.