TWI415894B - Functional resin composition - Google Patents

Abstract

The invention provides a functional resin composition, containing a poly lactic acid resin, a flame-proofing agent, a compatibilizer, a viscosity modifying agent, and a grafting agent. More particularly, the compatibilizer is selected from the chemical structure represented by the formula (I) that is defined by claims and the specification, for supporting and improving the compatibility of the poly lactic acid resin and flame-proof agent. The grafting agent is used for binding the compatibilizer and the poly lactic acid resin so as to increase the flame retardant durability of the functional resin. The biodegradable polymer represented by the formula (I) can simultaneously improve the whole mechanical property of the functional resin to obtain a functional resin composition having biodegradability and good flame retardant durability and impact resistance.

Description

Functional resin composition

The present invention relates to a functional resin composition, and more particularly to a functional resin composition having flame resistance.

Polymer materials generally prepared from petrochemical raw materials are widely used in many daily life products (such as building materials, packaging materials, household goods, mechanical parts, etc.) because of their excellent mechanical properties, but polymer materials. In the case of fire, it is easy to burn and cause a fire. In the process of combustion, a large amount of smoke and toxic gases are released, which causes air pollution. Since most of the polymer materials cannot be decomposed, they are used. Waste often causes damage to the environment again. Therefore, at present, the industry hopes that not only the shortcomings of flammability of polymer materials can be improved, but also the environmental pollution problem caused by the inability of polymer materials to be decomposed can be solved at the same time.

In order to solve the above-mentioned problems associated with polymer materials, a flame retardant is often added to a biodegradable polymer material to obtain a flame retardant and biodegradable polymer material.

However, most commonly used flame retardants contain halogens. In the Waste Electrical and Electronic Equipment (WEEE), the use of hazardous substances in electrical and electronic equipment is based on the hazardous substances. (Restriction of Hazardous Substance, RoHS) to regulate, in which halogen-containing flame retardants have been banned since July 31, 2006, so it is commonly used in the industry, and halogen-free flame retardants are mostly phosphorus-containing. Phosphorus-based flame retardant, aluminum hydroxide, magnesium hydroxide, or a combination thereof, however, the flame retardant added to the polymer material has a problem of compatibility with the polymer material for a long time. The use of the flame retardant will migrate to the surface of the polymer material, causing the loss of the flame retardant and the surface atomization of the polymer material, which not only affects the surface characteristics of the polymer material, but also easily causes the polymer material to be used for a long time. The problem of reduced flame resistance.

In addition, general biodegradable polymer materials, such as polylactic acid (PLAs) and polyhydroxyalkanoates (PHAs), can be decomposed by microorganisms in the natural environment to avoid general The problem of contamination of polymer materials made from petrochemical raw materials, however, the nature of these biodegradable resins themselves limits the development of products. Taking polylactic acid as an example, the glass transition temperature of polylactic acid is generally about 60 ° C, and the melting point can reach 160-170 ° C. However, since the crystallization rate of polylactic acid is very slow, the product obtained by polylactic acid has a temperature exceeding about 55. At °C, deformation occurs; on the other hand, the tensile strength of polylactic acid can reach 650~680Kg/cm ² , but its elongation is only 4~5%. From the above performance, it can be seen that the poly Lactic acid is not heat-resistant and impact-resistant. However, in many applications, it is not only required to have flame-resistant properties, but also heat resistance and impact resistance are the basic performance requirements of the product.

Therefore, under the rise of today's environmental awareness, how to find a kind of long-lasting fire resistance, no toxic gas will be produced when burning, and will not cause environmental burden, and at the same time have both heat resistance and impact resistance to replace the current petrochemical Environmentally friendly materials for polymer materials made from raw materials have been one of the active development directions of researchers in related fields.

Accordingly, it is an object of the present invention to provide a functional resin composition which has both flame retardancy and biodegradability.

Thus, a functional resin composition of the present invention comprises a polylactic acid resin having a molecular weight of between 35,000 and 250,000 and a weight percentage of between 75 wt% and 90 wt%, a selected from the group consisting of phosphorus-containing compounds, and a weight. The percentage is a flame retardant between 6 wt% and 12 wt%, a chemical structure having the following formula (I), the weight percentage is between 2 wt% and 8 wt%, and X is selected from the group consisting of high biodegradability a molecular compatibilizer, a weight percentage of between 2 wt% and 5 wt% of a viscosity modifier, and a grafting agent comprising at least one peroxide, the grafting agent is externally added, and the addition ratio is the above Between 0.5 wt% and 3 wt% of the sum of the weight percentages of the components.

The effect of the invention is that the fireproofing agent and the polylactic acid resin are connected to each other by adding a compatibilizing agent having a chemical structure as shown in the formula (I), and the polylactic acid resin is compatible with the grafting agent. The combination of the agents not only improves the compatibility of the fire retardant with the polylactic acid resin, but also increases the flame resistance durability of the functional resin, and the biodegradable polymer represented by the formula (I) can simultaneously enhance the functional resin as a whole. The mechanical properties provide a functional resin composition which is biodegradable and has excellent flame retardancy and impact resistance.

The functional resin composition of the present invention comprises a polylactic acid resin, a fireproofing agent, a compatibilizing agent, a viscosity adjusting agent, and a grafting agent.

The polylactic acid resin has a molecular weight ranging from 35,000 to 250,000, and the weight percentage is between 75 wt% and 90 wt%.

When the molecular weight of the polylactic acid resin is too low, the melting point is too low and the mechanical properties are not good, and it is impossible to form or obtain a finished product having an appropriate strength. When the molecular weight of the polylactic acid resin is too high, the melting point is too high. The processing property is not good. Therefore, preferably, the molecular weight of the polylactic acid resin is between 120,000 and 210,000.

The fire retardant is selected from the group consisting of phosphorus-containing compounds, and the weight percentage is between 6 wt% and 12 wt%, and the fire retardant used in the examples of the present invention is selected from triphenyl phosphate or phosphorus nitrogen compounds.

The compatibilizing agent has a chemical structure as shown in the formula (I), which is a graft of a maleic anhydride (MAH) molecule and a polymer segment (X), and the weight percentage of the compatibilizing agent is between 2% by weight and Between 8wt%.

The compatibilizing agent is obtained by linking a polylactic acid resin with a fire retardant by a maleic anhydride molecule in the structure of the formula (I) to increase the compatibility of the fire retardant with the polylactic acid resin, and at the same time, the structure of the formula (I) The polymer segment improves the compatibility of the compatibilizer with the polylactic acid resin, and reduces the amount of the fire retardant added, and the polymer segment X can simultaneously improve the mechanical properties of the functional resin, preferably The polymer segment X is a polymer selected from biodegradable polymers which are compatible with polylactic acid resins, such as polylactic acid (PLAs), thermoplastic polyurethane (TPU) ethers or The ester, the compatibilizer used in the examples of the present invention is a graft compound of maleic anhydride and a thermoplastic polyurethane (MAG-g-TPU).

The viscosity adjuster is between 2% by weight and 5% by weight, and the viscosity of the functional resin composition can be appropriately adjusted to improve the processability. The viscosity adjusting agent used in the embodiment of the present invention is A compound selected from the group consisting of magnesium oxide and cerium oxide (3MgO‧4SiO2‧H2O).

The grafting agent comprises at least one peroxide, which is externally added, and the addition ratio is between 0.5% by weight and 3% by weight of the sum of the weight percentages of the above components, for carrying out the polylactic acid resin and the compatibilizing agent. link.

Preferably, the grafting agent is selected from the group consisting of benzammonium peroxide and bisperoxyisopropyl peroxide, and the grafting agent used in the examples of the present invention is selected from the group consisting of benzoquinone peroxide. And a combination of bisperoxyisopropyl peroxide, and the combination ratio thereof is 3:1.

The reaction characteristics can be cleavable by using benzoic acid benzoquinone at about 70 ° C, and simultaneously with the addition of bisperoxy isopropyl peroxide having a high temperature bridging reaction (thermal cracking temperature of about 105 to 120 ° C), The functional resin composition improves the grafting ratio of the polylactic acid resin and the compatibilizing agent in the high-temperature processing process, and not only reduces the residual amount of the grafting agent, but also improves the grafting efficiency.

By adding a compatibilizing agent and a grafting agent having a chemical structure as shown in the above formula (I), not only the fireproofing agent, the polylactic acid resin and the compatibilizing agent can be connected to each other, but also the fireproofing agent, the compatibilizing agent and the polylactic acid resin can be improved. The compatibility of the resin reduces the problem that the fire retardant migrates to the surface of the polymer material due to long-term use, and can increase the durability of the functional resin, and can simultaneously improve the function of the polymer segment in the structure of the formula (I) The mechanical properties of the resin provide a functional resin composition which is biodegradable and has excellent flame retardancy and mechanical properties.

The functional resin composition of the present invention can be directly blended or prepared by other conventional means to obtain a functional resin having the above components.

In the embodiment of the present invention, an appropriate amount of each functional resin composition is first weighed, and then each functional resin composition is separately mixed in a tower mixer at about 25 to 30 ° C for 30 minutes, and then The pelletized functional resin was obtained by extrusion at 160 to 180 ° C using a twin-screw extruder.

<Example>

The functional resin composition of the present invention can be applied to building materials, packaging materials, household goods, mechanical parts, etc., and the present invention will be described in the following embodiments, but it should be understood that the embodiments are for illustrative purposes only. It should not be construed as limiting the invention.

<chemicals>

1. Polylactic acid resin: The molecular weight is 210,000, manufactured by Weimeng Company, and the product name is 2100.

2. Fire retardant: Triphenyl phosphate (hereinafter referred to as TPP, product name: TPPS), phosphorus nitrogen compound (hereinafter referred to as PN, product name: PN30), manufactured by Changchun Company.

3. Compatibilizer: Thermoplastic polyurethane and maleic anhydride graft compound (hereinafter referred to as TPU-g-MAH), manufactured by Kanda Corporation, and named R10.

4. Grafting agent: benzoic acid peroxide (hereinafter referred to as BPO), bisperoxy isopropyl peroxide (hereinafter referred to as DCP), manufactured by Yankai Company, and the product name is BPO, DCP.

5. Viscosity modifier: manufactured by Xinsheng Company, the name is magnesium powder (magnesium oxide, cerium oxide, 3MgO‧4SiO ₂ ‧H2O).

<Specific example 1>

First, weighed 79 grams of polylactic acid resin, 11 grams of fire retardant (TPP), 7 grams of compatibilizer, 3 grams of viscosity modifier, and 0.5 grams of external grafting agent, stirred at 25 ~ 30 ° C for 30 minutes, then Further, the functional resin composition is extruded at 160 to 180 ° C by a twin-screw extruder to obtain a functional resin in a granular form.

<Specific examples 2 to 10>

The components of the different ratios were changed, and the same production method as that of the specific example 1 was carried out, and finally the functional resins of Specific Examples 2 to 10 were obtained.

<Comparative Example 1>

88 g of polylactic acid resin, 8 g of a fire retardant (TPP), and 4 g of a viscosity modifier were weighed. The same procedure as in Example 1 was carried out, and finally the functional resin of Comparative Example 1 was obtained.

<Comparative Example 2>

89 g of a polylactic acid resin, a fireproofing agent (PN) of 8 g, and a viscosity adjuster of 4 g were weighed, and the same procedure as in the specific example 1 was carried out, and finally, the functional resin of Comparative Example 2 was obtained.

The composition ratios of the functional components of the functional resins obtained in Specific Examples 1 to 10 and Comparative Examples 1 and 2 are shown in Table 1.

<test>

The functional resins of Examples 1 to 10 and Comparative Examples 1 and 2 of the same weight were respectively taken, and the following tests were carried out after being injected into a standard test piece. The final test results are shown in Table 2 below: Flame retardancy test: According to UL -94 standard method for test piece production and testing, the standard thickness of the test piece is 1/8mm and 1/16mm respectively, and the test results according to the flame retardant property are classified into "V- according to the flame resistance performance. 0′′, “V-1”, “V-2” and “NG”; the test piece of the present invention is made of 1/16 mm, and the first flame-retardant test is performed when the test piece is prepared (the test result is "0month" is indicated, and after being placed in an environment of 25 ° C and a relative humidity of 50 RH% for 18 months, the surface of the test piece is wiped clean with a dust-free cloth, and a second flame-retardant test is performed (the test result is "18month" ”)), and after being placed in an environment of 25°C and relative humidity of 50RH% for 24 months, wipe the surface of the test piece with a dust-free cloth and perform the third time of the flame-retardant test (the test result is “24month”) Express).

Impact strength (IZOD, Kg/cm ² ) test: Test piece production and test of notch impact according to the standard method of ASTM D638.

Flexural strength (Kg/cm ² ) test: The test piece was produced and tested for maximum strength according to the standard method of ASTM D790.

Table 2 shows the test results of the test pieces prepared in the above respective examples.

It can be seen from the test results of Comparative Examples 1 and 2 in Table 2 that when only the polylactic acid resin and the fire retardant are used in the system of the functional resin composition, not only the flame retardancy and the flame retardant durability are poor, but also the bending strength is obtained. The performance was also poor (260 Kg/m ² ); and the test results of Examples 1 to 10 showed that when the compatibilizer and the grafting agent were added to the polylactic acid resin/fire retardant system, the amount of the fire retardant added was 7 wt%. The UL94-V-0 rating can be achieved, and the flame retardancy can be effectively maintained after 24 months of storage. The test results of the flexural strength also show that the addition of the compatibilizer can also be effective. Improve its bending strength (282~332Kg/m ² ).

In summary, the functional resin composition of the present invention connects the fireproofing agent and the polylactic acid resin to each other by adding a compatibilizing agent having a chemical structure as shown in the formula (I) to enhance the fireproofing agent and the polylactic acid resin resin. Compatibility, and at the same time, by combining the polylactic acid resin with a compatibilizing agent by a grafting agent, not only can the flame retardant be prevented from migrating to the surface to cause loss of the fire retardant, and the polymer represented by the formula (I) is also The mechanical properties of the functional resin as a whole can be simultaneously improved, and a functional resin composition which is biodegradable, has excellent flame retardancy durability and good bending strength can be obtained.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

Claims (5)

A functional resin composition comprising: a polylactic acid resin having a molecular weight ranging from 35,000 to 250,000 and a weight percentage of between 75 wt% and 90 wt%; a fire retardant selected from the group consisting of phosphorus compounds, weight percent Is between 6wt% and 12wt%; a compatibilizer having a chemical structure of formula (I), and the weight percentage is between 2wt% and 8% by weight, And X is selected from a biodegradable high molecular polymer, which can be used to assist in improving the compatibility of the polylactic acid resin and the fireproofing agent; a viscosity adjusting agent, the weight percentage is between 2% by weight and 5% by weight, and can be used Adjusting the viscosity of the functional resin composition; and a grafting agent comprising at least one peroxide, the grafting agent is externally added, and the added amount is the polylactic acid resin, the fireproofing agent, the compatibilizing agent, and the viscosity adjustment From 0.5% by weight to 1% by weight based on the total weight percentage of the agent, the compatibilizing agent and the polylactic acid resin may be combined with each other. The functional resin composition according to claim 1, wherein the polylactic acid resin has a molecular weight ranging from 120,000 to 210,000. The functional resin composition according to claim 1, wherein the compatibilizing agent is selected from the group consisting of thermoplastic polyurethanes. The functional resin composition according to claim 3, wherein the grafting agent is a combination selected from the group consisting of benzodiazepine and bisperoxyisopropyl peroxide. The functional resin composition according to claim 1, wherein the fire retardant is selected from the group consisting of triphenyl phosphate and a phosphorus nitrogen compound.