KR20180014912A - Multi functional additive agent for polymers and method for preparing the same - Google Patents

Abstract

The present invention relates to a multifunctional additive for polymers represented by chemical formula 1 and a method for preparing the same and, more specifically, to a multifunctional additive for polymers capable of improving flowability, light stability, interfacial adhesion between a base resin and a reinforced fiber in a reinforced fiber plastic, etc. while not reducing basic physical properties of an added polymer resin, and to a method for preparing the same.

Description

TECHNICAL FIELD The present invention relates to a multifunctional functional additive for polymers and a method for preparing the same,

The present invention relates to a multifunctional functional additive for a polymer and a method for producing the same. More specifically, the present invention relates to a multi-functional additive for polymers capable of simultaneously improving fluidity, optical stability, interfacial adhesion between a base resin and reinforcing fibers in a fiber-reinforced plastic without deteriorating the basic physical properties of the polymer resin to be added, And a manufacturing method thereof.

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, a multifunctional functional additive for polymers and a method for producing the same that are 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 are desperately required In fact.

It is an object of the present invention to provide a multifunctional functional additive for polymers capable of simultaneously improving 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 and a method for producing the same .

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

In order to solve the above problems,

There is provided a multifunctional functional additive for a polymer having a structure represented by the following general 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 a functional group having -OH or a hindered amine unit of formula (2) or (3) below.

(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 are each independently a functional group of Formula 2, C _{1 -18} alkoxy group, a C _{3 -5} deugi epoxy, or halogen, C _{1 -5} alkoxy group, may be substituted with a carbonyl group, carbamoyl group, or an alkoxycarbonyl group Lt; / RTI >

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

Wherein A is -NH-, R ₁ is -CH ₃ , R ₂ is hydrogen (H), and R ₅ and R ₆ are both functional groups of formula (2), wherein A is -NH- , R ₁ is -CH ₃ , and R ₂ is hydrogen).

Also provided is a multifunctional functional 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 the multifunctional functional additive for a polymer according to the first aspect, wherein the compound of the general formula (5), the compound of the general formula (6), the compound of the general formula (7) or both are subjected to a dehydration condensation reaction at a high temperature.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,

x, y, R ₁ , R ₂ , R ₅ and R ₆ are the same as those in the above formulas (1) to (4)

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.

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 of the above-mentioned 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 alkoxycarbonyl group Lt; / RTI >

The present invention also provides a process for preparing the multifunctional functional additive for a polymer according to the first aspect, wherein the compound of the formula (8) is a compound of the following formula (10).

[Chemical formula 10]

In Formula 10,

R ₇ is C _{1 -20} alkyl, C _{1 -20} alkyl amino, C _{1 -20} alkyl substituted amino, C _{1 -20-hydroxy-alkyl,} C _{1 -20} alkenyl, substituted C _{1 -20} alkenyl, alkoxyalkyl group, C _{1 -20-oxy} -NC _{1 -20} alkyl, C _{1 -10} -N- cycloalkyl group or -COR ₁₂ (wherein, R ₁₂ is hydrogen, C _{1 -6} alkyl, phenyl, C _{1 -20} COO (H or C ₁ is a C _{1 -10} -N- cycloalkyl group substituted by a _{4-alkyl), -}

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.

The method for preparing the multifunctional additive for polymers according to claim 1, wherein the compound of 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 multifunctional functional additive for the polymer is provided.

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

The multifunctional functional additive for polymers according to the present invention exhibits excellent effects in that the flowability, optical stability, interfacial adhesion with a reinforcing material, and the like of the polymer resin can be remarkably improved by a specific molecular structure at the same time.

Also, the multifunctional functional additive for polymers 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 the 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 multifunctional functional 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 chemical formula 1, Lt; / RTI >

[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 a functional group having -OH or a hindered amine unit of formula (2) or (3) below.

(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 are each independently a functional group of Formula 2, C _{1 -18} alkoxy group, a C _{3 -5} deugi epoxy, or halogen, C _{1 -5} alkoxy group, may be substituted with a carbonyl group, carbamoyl group, or an alkoxycarbonyl group And preferably all of the functional groups of 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 multifunctional functional additive for a polymer of Formula 1 according to the present invention may be prepared by subjecting a compound of Chemical Formula 5, a compound of Chemical Formula 6 below, a compound of Chemical Formula 7 or all of them to a dehydration condensation reaction at a high temperature, for example, 200 ° C .

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,

x, y, R ₁ , R ₂ , R ₅ and R ₆ are the same as those in the above formulas (1) to (4)

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 of the above-mentioned 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 alkoxycarbonyl group Lt; / RTI >

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 C _{1 -20} alkyl, C _{1 -20} alkyl amino, C _{1 -20} alkyl substituted amino, C _{1 -20-hydroxy-alkyl,} C _{1 -20} alkenyl, substituted C _{1 -20} alkenyl, alkoxyalkyl group, C _{1 -20-oxy} -NC _{1 -20} alkyl, C _{1 -10} -N- cycloalkyl group or -COR ₁₂ (wherein, R ₁₂ is hydrogen, C _{1 -6} alkyl, phenyl, C _{1 -20} COO (H or C ₁ is a C _{1 -10} -N- cycloalkyl group substituted by a _{4-alkyl), -}

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 multifunctional functional additive for a 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 polymer composite material comprising the above-described complex functional additive for a polymer of Formula 1 and a polymer resin. Here, the content of the multi-functional additive for 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 the multifunctional 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 Multifunctional functional 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 multifunctional additive for polymer of Formula 1 according to the present invention have excellent fluidity and at the same time exhibit excellent optical stability, interfacial adhesion between the polymer resin and the reinforcement The mechanical strengths such as tensile strength, flexural strength, flexural modulus and impact strength were all improved. On the other hand, Comparative Example 1 of the polymer composite material without the multifunctional functional additive for polymer of the above formula (1) And the mechanical strengths such as tensile strength, flexural strength, flexural modulus and impact strength were all 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 multi-functional 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 a functional group having -OH or a hindered amine unit of formula (2) or (3) below.
(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 containing an oxygen (O) atom or another nitrogen (N) atom, preferably forming a functional group from piperidine or morpholine,
R ₅ and R ₆ are each independently a functional group of Formula 2, C _{1 -18} alkoxy group, a C _{3 -5} deugi epoxy, or halogen, C _{1 -5} alkoxy group, may be substituted with a carbonyl group, carbamoyl group, or an alkoxycarbonyl group Lt; / RTI >
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 of formula 2, 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 complex functional additive for a polymer according to claim 1, wherein the compound of the general formula (5), the compound of the general formula (6), the compound of the general formula (7) or both are dehydrated and condensed at a high temperature.
[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,
x, y, R ₁ , R ₂ , R ₅ and R ₆ are the same as those in the above formulas (1) to (4)
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. 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 of the above-mentioned 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 alkoxycarbonyl group Lt; / RTI > 6. The method of claim 5,
The method for producing a complex functional 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 C _{1 -20} alkyl, C _{1 -20} alkyl amino, C _{1 -20} alkyl substituted amino, C _{1 -20-hydroxy-alkyl,} C _{1 -20} alkenyl, substituted C _{1 -20} alkenyl, alkoxyalkyl group, C _{1 -20-oxy} -NC _{1 -20} alkyl, C _{1 -10} -N- cycloalkyl group or -COR ₁₂ (wherein, R ₁₂ is hydrogen, C _{1 -6} alkyl, phenyl, C _{1 -20} COO (H or C ₁ is a C _{1 -10} -N- cycloalkyl group substituted by a _{4-alkyl), -}
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. 6. The method of claim 5,
The method of 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 multifunctional functional additive for a polymer according to any one of claims 1 to 3. 9. The method of claim 8,
Wherein the content of the multifunctional functional additive for polymer is 0.1 to 1.0 wt% based on the total weight of the polymer composite material.