KR101993033B1 - Flowable additive agent for polymers and method for preparing the same - Google Patents

Abstract

The present invention relates to a flowable additive for a polymer and a method for producing the same. Specifically, the present invention relates to a flowable additive for polymers capable of simultaneously improving fluidity, optical stability, interfacial adhesion between a base resin and a reinforcing fiber in a fiber-reinforced plastic without deteriorating the basic physical properties of the polymer resin to be added, ≪ / RTI >

Description

TECHNICAL FIELD [0001] The present invention relates to a flowable additive for a polymer and a method for preparing the same,

The present invention relates to a flowable additive for a polymer and a method for producing the same. Specifically, the present invention relates to a flowable additive for polymers capable of simultaneously improving fluidity, optical stability, interfacial adhesion between a base resin and a reinforcing fiber in a fiber-reinforced plastic without deteriorating the basic physical properties of the polymer resin to be added, ≪ / RTI >

The polymer resin may be mixed with various kinds of additives to improve the insufficient physical properties or the physical properties required depending on the application to be used.

Particularly, a polyamide resin is a synthetic resin widely used for producing yarns, fibers and filaments, and may have insufficient flowability when it is formed into a molded product having a complicated shape, and may be deteriorated or decomposed by light such as ultraviolet rays , And reinforcing materials such as glass fiber or carbon fiber are mixed and used as fiber reinforced plastic, the interfacial adhesion with the reinforcing material is insufficient, so that the reinforcing material can not be uniformly mixed in the resin, and consequently, the reinforcing effect is hardly realized.

Therefore, a fluidity-improving agent, a stabilizer, a coupling agent, and the like may be optionally added to the polyamide resin. When a large amount of various additives is added, the basic properties of the polyamide resin may be significantly deteriorated or the effect of additives may be improved And when the polyamide composite material is produced by incorporating two or more additives into the polyamide resin, the manufacturing process may be complicated or the manufacturing cost may increase.

Therefore, there is a desperate need for a fluidity additive for polymers and a method for producing the same which can improve fluidity, optical stability, interfacial adhesion between a base resin and a reinforcing fiber at the same time without deteriorating the basic physical properties of the polymer resin It is true.

Patent Document 10-2015-0081027 (Jul. 13, 2015)

The present invention aims to provide a flowable additive for polymers and a method for producing the same, which can simultaneously improve fluidity, optical stability, interfacial adhesion with a reinforcing material and the like of the resin without deteriorating the basic physical properties of the polymer resin.

Another object of the present invention is to provide a flowable additive for a polymer which can simplify the production process of a polymer composite material and can reduce manufacturing cost, and a method for producing the same.

In order to solve the above problems,

There is provided a flowable additive for a polymer having a structure represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

x is from 100 to 5,000,

y is from 5 to 250,

z is from 5 to 250,

R and R 'are each independently -OH or a functional group having a hindered amine unit of the following formula (2) or a functional group of the formula (3).

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

P is 0 or 1,

A is -O- or -NR < ₂ > -,

R ₁ is alkyl to form a ring each independently C _{1 -18} alkyl, or two of R ₁ is C _{4 -8} sayikeu,

R ₂ is hydrogen (H), C _{1 -12} alkyl groups, each independently, C _{1 -8} alkoxy group, -COR ₉ (wherein, R ₉ is hydrogen or C _{1 -6} alkyl), phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _{1 -12} alkyl, C _{5 -6} cycloalkyl group, or a phenyl group or C _{1 -12} alkyl group nitrogen (N) Together with the atoms form a 5 to 7 membered ring comprising an oxygen (O) atom or another nitrogen (N) atom, preferably forming a functional group from a piperidine or morpholine group,

R ₅ and R ₆ each independently represent a functional group having a hindered amine unit represented by the formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, or a halogen, a C _1-5 alkoxy group, a carbonyl group, a carbamyl group or an alkoxy An alkylamino group substituted or unsubstituted with a carbonyl group,

R ₅ 'is a functional group of formula (4) or a divalent functional group derived from the functional group of R ₅ .

Here, P is 0, A is -NH-, and R ₁ is a -CH _3, R ₂ is the functional group is hydrogen (H), both R ₅ and R ₆ having the hindered amine unit of formula (2) (wherein, A is -NH-, R ₁ is -CH ₃ , and R ₂ is hydrogen.

Also provided is a fluidity additive for a polymer characterized by having a molecular weight of 3,000 to 10,000.

The present invention also provides a process for producing a fluidity additive for a polymer, which comprises subjecting a compound of the formula (5) and a compound of the formula (5) or a compound of the formula (5) and a compound of a formula (7) or a compound of a formula (5) to a condensation reaction at a high temperature.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,

x, R ₁ , R ₂ , R ₅ and R ₆ are the same as in the above formulas (1) to (4)
w is from 10 to 500,

R ₃ and R ₄ are each independently hydrogen (H), C _{1 -12} alkyl, C _{1 -8} alkoxy group, -COR ₉ (wherein, R ₉ is hydrogen or C _{1 -6} alkyl), phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _{1 -12} alkyl, C _{5 -6} cycloalkyl, phenyl or C _1-12 alkyl phenyl group or nitrogen (O) or another nitrogen (N) atom together with a nitrogen atom to form a 5- to 7-membered ring, preferably forming a functional group from piperidine or morpholine.

Herein, the compound of formula (7) is a compound of the following formula (8) or (9).

[Chemical Formula 8]

[Chemical Formula 9]

In the general formulas (8) and (9)

R ₅ and R ₆ are each independently a functional group having a hindered amine unit of the above formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, or a halogen, a C _1-5 alkoxy group, a carbonyl group, An alkylamino group which is unsubstituted or substituted with an alkoxycarbonyl group.

Also, the present invention provides a process for preparing a flowable additive for a polymer, wherein the compound of the formula (8) is a compound of the following formula (10).

[Chemical formula 10]

In Formula 10,

R ₇ is a functional group having a hindered amine unit of the above formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, a halogen, a C _1-5 alkoxy group, a carbonyl group, a carbamyl group or an alkoxycarbonyl group,

R ₈ is hydrogen (H), C _{1 -12} alkyl groups, each independently, C _{1 -8} alkoxy group, -COR ₉ (wherein, R ₉ is hydrogen or C _{1 -6} alkyl), phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _{1 -12} alkyl, C _{5 -6} cycloalkyl group, or a phenyl group or C _{1 -12} alkyl group nitrogen (N) Together with the atoms form a five to seven-membered ring comprising an oxygen (O) atom or another nitrogen (N) atom, preferably forming a functional group from a piperidine or morpholine.

Also, the present invention provides a process for preparing a flowable additive for a polymer, wherein the compound of the formula (8) is a compound of the following formula (11).

(11)

On the other hand, a polymer composite material comprising a polymer resin and a fluidity additive for the polymer is provided.

Here, the content of the flowable additive for a polymer is 0.1 to 1.0 wt% based on the total weight of the polymer composite material.

The flowable additive for polymers according to the present invention exhibits excellent effects that can remarkably improve flowability, optical stability, interfacial adhesion with a reinforcing material and the like due to a specific molecular structure.

Further, the flowable additive for polymer according to the present invention has an excellent effect of simplifying the production process of the polymer composite produced by incorporating the additive and reducing manufacturing cost.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

The present invention relates to a flowable additive for polymers capable of simultaneously improving fluidity, optical stability, interfacial adhesion with a reinforcing material, and the like of a polymer resin, and can have a molecular structure represented by the following formula (1) .

[Chemical Formula 1]

In Formula 1,

x is from 100 to 5,000,

y is from 5 to 250,

z is from 5 to 250,

R and R 'are each independently -OH or a functional group having a hindered amine unit of the following formula (2) or a functional group of the formula (3).

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

P is 0 or 1, preferably 0,

A is -O- or -NR ₂ -, and, preferably -NH-,

R ₁ are each independently C _{1 -18} alkyl, or two R ₁ is C _{4 -8} sayikeu is to form an alkyl ring, and preferably -CH _3,

R ₂ is hydrogen (H), C _{1 -12} alkyl groups, each independently, C _{1 -8} alkoxy group, -COR ₉ (wherein, R ₉ is hydrogen or C _{1 -6} alkyl), phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _{1 -12} alkyl, C _{5 -6} cycloalkyl group, or a phenyl group or C _{1 -12} alkyl group nitrogen (N) Together with the atoms form a 5- to 7-membered ring containing an oxygen (O) atom or another nitrogen (N) atom, preferably forming a functional group from a piperidine or morpholine group, Hydrogen (H)

R ₅ and R ₆ each independently represent a functional group having a hindered amine unit represented by the formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, or a halogen, a C _1-5 alkoxy group, a carbonyl group, a carbamyl group or an alkoxy Is an alkylamino group which is unsubstituted or substituted with a carbonyl group and is preferably a functional group having a hindered amine unit represented by the general formula (2) wherein A is -NH-, R ₁ is -CH ₃ and R ₂ is hydrogen.

R ₅ 'is a functional group of formula (4) or a divalent functional group derived from the functional group of R ₅ .

The fluidity additive for a polymer of Formula 1 according to the present invention may be prepared by reacting a compound of Formula 5 below, a compound of Formula 6 below, a compound of Formula 5 below, a compound of Formula 7 or a compound of Formula 5 to 7 below at a high temperature, And condensation reaction at a temperature of 200 ° C.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,

x, R ₁ , R ₂ , R ₅ and R ₆ are the same as in the above formulas (1) to (4)
w is from 10 to 500,

R ₃ and R ₄ are each independently hydrogen (H), C _{1 -12} alkyl, C _{1 -8} alkoxy group, -COR ₉ (wherein, R ₉ is hydrogen or C _{1 -6} alkyl), phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _{1 -12} alkyl, C _{5 -6} cycloalkyl, phenyl or C _1-12 alkyl phenyl group or nitrogen (O) or another nitrogen (N) atom together with a nitrogen atom to form a 5- to 7-membered ring, preferably forming a functional group from piperidine or morpholine.

The compound of formula (7) may be a compound of formula (8) or (9) when P is 0.

[Chemical Formula 8]

[Chemical Formula 9]

In the general formulas (8) and (9)

R ₅ and R ₆ are each independently a functional group having a hindered amine unit of the above formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, or a halogen, a C _1-5 alkoxy group, a carbonyl group, An alkylamino group which is unsubstituted or substituted with an alkoxycarbonyl group.

Here, the compound of formula (8) may be a compound of formula (10) below, more preferably a compound of formula (11) below.

[Chemical formula 10]

In Formula 10,

R ₇ is a functional group having a hindered amine unit of the above formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, a halogen, a C _1-5 alkoxy group, a carbonyl group, a carbamyl group or an alkoxycarbonyl group,

R ₈ is hydrogen (H), C _{1 -12} alkyl groups, each independently, C _{1 -8} alkoxy group, -COR ₉ (wherein, R ₉ is hydrogen or C _{1 -6} alkyl), phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _{1 -12} alkyl, C _{5 -6} cycloalkyl group, or a phenyl group or C _{1 -12} alkyl group nitrogen (N) Together with the atoms form a five to seven-membered ring comprising an oxygen (O) atom or another nitrogen (N) atom, preferably forming a functional group from a piperidine or morpholine.

(11)

In particular, the fluidity additive for the polymer of Formula 1 according to the present invention can be prepared by the following Reaction Scheme 1.

[Reaction Scheme 1]

The present invention also relates to a polymeric composite material comprising the above-described flowable additive for a polymer of Formula 1 and a polymer resin. Here, the content of the flowable additive for the polymer of Formula 1 may be 0.1 to 1% by weight based on the total weight of the polymer composite.

[Example]

1. Manufacturing Example

As shown in Table 1 below, polymer composite specimens were prepared by mixing nylon-66 resin, glass fiber, and fluidity additive for polymer of Formula 1 according to the present invention.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Nylon-66 resin (g) 70 70 70 70 70 Glass fiber (g) 30 30 30 30 30 Flowable additive for polymer (% by weight) 0.2 0.3 0.5 1.0 0

2. Property evaluation

The melt index of the polymer composite, the tensile strength, the flexural strength, the flexural modulus and the impact strength of the polymer composite specimens were measured for each of Examples and Comparative Examples, and the measurement results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 The melt index (g / 10 min, 250 캜) 16.80 17.30 18.60 19.20 16.20 Tensile strength (N / mm 2) 1,598 1,667 1,684 1,687 1,579 Flexural Strength (N / mm2) 2,559 2,625 2,725 2,773 2,573 Flexural modulus (kg / cm2) 87,572 87,635 89,680 93,138 81,857 Impact strength (N / ㎟) 10.10 10.80 11.20 11.80 9.80

As shown in Table 2, Examples 1 to 4 of the polymer composite material containing the flowable additive for polymer of Formula 1 according to the present invention are excellent in fluidity and have excellent light stability, And the mechanical strengths such as tensile strength, flexural strength, flexural modulus and impact strength were all improved. On the other hand, in Comparative Example 1 of the polymer composite without the fluidity additive for polymer of Formula 1, Tensile strength, flexural strength, flexural modulus, impact strength, and the like were all found to be lowered.

While the present invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. . It is therefore to be understood that the modified embodiments are included in the technical scope of the present invention if they basically include elements of the claims of the present invention.

Claims (9)

A flowable additive for a polymer having a structure represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
x is from 100 to 5,000,
y is from 5 to 250,
z is from 5 to 250,
At least one of R and R 'is a functional group of the following formula (3) and the remainder is a functional group having -OH or a hindered amine unit of the following formula (2).
(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,
P is 0 or 1,
A is -O- or -NR < ₂ > -,
Each R ₁ is independently a C _1-18 alkyl group, or two R ₁ form a C _4-8 cycloalkyl ring,
R ₂ is each independently selected from the group consisting of hydrogen (H), C _1-12 alkyl group, C _1-8 alkoxy group, -COR ₉ wherein R ₉ is hydrogen or C _1-6 alkyl, phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl group, a phenyl group or a C _1-12 alkyl group or a nitrogen (N) (O) or another nitrogen (N) atom together with the nitrogen atom to which they are attached form a 5 to 7 membered ring,
R ₅ and R ₆ each independently represent a functional group having a hindered amine unit represented by the formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, or a halogen, a C _1-5 alkoxy group, a carbonyl group, a carbamyl group or an alkoxy An alkylamino group which is unsubstituted or substituted with a carbonyl group,
R ₅ 'is a functional group of formula (4) or a divalent functional group derived from the functional group of R ₅ . The method according to claim 1,
P is 0, A is -NH-, R ₁ is -CH ₃ , R ₂ is hydrogen (H), R ₅ and R ₆ are both functional groups having a hindered amine unit of formula 2, -NH-, R ₁ is -CH ₃ , and R ₂ is hydrogen. 3. The method according to claim 1 or 2,
And a molecular weight of 3,000 to 10,000. A process for producing a flowable additive for a polymer according to claim 1, wherein the compound of the formula (5) and the compound of the formula (7) or the compounds of the formulas (5) to (7) are subjected to a condensation reaction at a high temperature of 200 ° C.
[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,
x, R ₁ , R ₂ , R ₅ , R ₆ and P are the same as defined in the above Chemical Formulas 1 to 4,
w is from 10 to 500,
R ₃ and R ₄ are each independently selected from the group consisting of hydrogen (H), C _1-12 alkyl group, C _1-8 alkoxy group, -COR ₉ wherein R ₉ is hydrogen or C _1-6 alkyl, (C _1-4 alkyl) or -NR ₁₀ R ₁₁ wherein R ₁₀ and R ₁₁ are each independently hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl, phenyl or a C _1-12 alkylphenyl group or nitrogen (O) or another nitrogen (N) atom together with the nitrogen atom to which they are attached. 5. The method of claim 4,
The method of claim 1, wherein the compound of formula (7) is a compound of the following formula (8) or (9).
[Chemical Formula 8]

[Chemical Formula 9]

In the general formulas (8) and (9)
R ₅ and R ₆ are each independently a functional group having a hindered amine unit of the above formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, or a halogen, a C _1-5 alkoxy group, a carbonyl group, An alkylamino group which is unsubstituted or substituted with an alkoxycarbonyl group. 6. The method of claim 5,
The process for producing a flowable additive for a polymer according to claim 1, wherein the compound of formula (8) is a compound of the following formula (10).
[Chemical formula 10]

In Formula 10,
R ₇ is a functional group having a hindered amine unit of the above formula (2), a C _1-18 alkoxy group, a C _3-5 epoxide group, a halogen, a C _1-5 alkoxy group, a carbonyl group, a carbamyl group or an alkoxycarbonyl group,
R ₈ is each independently selected from the group consisting of hydrogen (H), C _1-12 alkyl group, C _1-8 alkoxy group, -COR ₉ wherein R ₉ is hydrogen or C _1-6 alkyl, phenyl, -COO (C _{1 -4} alkyl) or -NR ₁₀ R ₁₁ (wherein, R ₁₀ and R ₁₁ are each independently hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl group, a phenyl group or a C _1-12 alkyl group or a nitrogen (N) (O) or another nitrogen (N) atom together with the nitrogen atom to which they are attached form a 5 to 7 membered ring. 6. The method of claim 5,
The process for producing a flowable additive for a polymer according to claim 1, wherein the compound of formula (8) is a compound of the following formula (11).
(11)

A polymer composite material comprising a polymer resin and a flowable additive for a polymer according to any one of claims 1 to 3. 9. The method of claim 8,
Wherein the content of the flowable additive for the polymer is 0.1 to 1.0% by weight based on the total weight of the polymer composite material.