KR101328913B1 - Method for preparation of modified polyolefin for polyolefin compatibilizer - Google Patents

Abstract

The present invention relates to a method for preparing a modified polyolefin by using a polyolefin-based resin. The method dissolves a polyolefin resin in a solvent, injects an organic radical initiator and an unsaturated hydrocarbon-containing additives to manufacture a modified polyolefin precursor, and makes the precursor reacts with polyether amine. The method can easily control the content of polar functional groups.

Description

METHODS FOR PREPARATION OF MODIFIED POLYOLEFIN FOR POLYOLEFIN COMPATIBILIZER}

The present invention relates to a method for producing a modified polyolefin capable of easily introducing various polar functional groups while varying the content of the functional functional groups in introducing the functional functional groups into the polyolefin resin.

In general, polyolefin resins have excellent mechanical properties, optical properties, chemical properties, and moldability, and are advantageous in terms of cost, and have been used in a wide range. However, polyolefin resins consisting essentially of hydrocarbons are non-polar materials, and have relatively low chemical reactivity compared to resins containing relatively polar functional groups, and have low compatibility with other types of resins. In addition, there is a limit in improving the properties of thermal adhesiveness, printing, coating and the like. Part of the attempt to solve this problem is to introduce a polar functional group to the non-polar polyolefin resin, through which the compatibility of the polyolefin and other resins can be increased, it can be used in various applications.

In the method of introducing the polar functional group, the polyolefin main chain is activated using various organic initiators or radioactivity, and then the polar functional group is introduced into the non-polar polyolefin in the form of a polyolefin copolymer or graft through reaction with the polar functional group. More specifically, as a method for producing a polyolefin compatibilizer having a polar functional group, there are largely a method of grafting a polar functional group using an extruder, a method of grafting in a solid phase, and a method of grafting a polar monomer in a solution state.

In the case of the manufacturing method using an extruder, the time required for production of the product is short, but the amount of the monomer is grafted to the product is small and is carried out under high temperature reaction conditions, there is a disadvantage that can not remove the unreacted material. In this regard, U.S. Patent No. 4,612,255 describes a method for designing various screw shapes and effectively carrying out the reaction of polyolefins and polar functional groups in a reaction extrusion reaction using a twin screw extruder. In addition, U.S. Patent Nos. 4,762,890 and 4,927,888 also suggest the reaction of the screw type polyolefin and the polar functional group in the extruder, and use various types of screw type extrusion conditions in the extruder, and the polyolefin and the reaction initiator, the polar functional group. In the course of the reaction with coagent, a method of increasing the ratio of polar functional groups in the resin is mentioned. U.S. Patent No. 47399 discloses a method for grafting in an extruder, in which various auxiliaries added during the reaction of the polyolefin and the polar functional group are used in various ways to effectively increase the graft efficiency.

On the other hand, as disclosed in Korean Patent Application No. 1999-0009389, the method of grafting in a solid phase is a method of grafting a polyolefin in a swollen state in which it is swelled with a solvent in a solid state. There is a disadvantage that the use is limited depending on the particle size of the polyolefin to be used.

In contrast, the method of grafting in solution state can obtain a relatively high graft content compared to the aforementioned methods, easy removal of unreacted functional groups, and at a relatively low temperature compared to commercially available extrusion methods. It has the advantage of proceeding the reaction, but is currently limited to some functional groups such as maleic anhydride, such as US Patent Publication No. 2009/0068483.

The method using the extruder, the graft copolymer by the solid phase graft method and the solution phase graft method is mainly benzoyl peroxide, dicumyl peroxide, etc. which are organic peroxides as reaction initiators in main chains such as polypropylene and polyethylene. And chemically grafted using polar functional groups such as acrylic acid, maleic acid, and maleic anhydride, are generally known methods, and the physical properties of the graft rate vary.

The present invention is to solve the problems of the prior art, such as the low graft rate and high temperature conditions, difficult to remove excess functional monomers accompanying the production of modified polyolefin by the conventional extrusion method as described above, An object of the present invention is to prepare a modified polyolefin having various functional functional groups in order to increase the compatibility with a resin having a polar functional group of a nonpolar polyolefin resin such as polyethylene and polypropylene, and thus the graft ratio can be increased. It is to provide a method for producing a modified polyolefin useful as a polyolefin compatibilizer capable of easily introducing various functional groups.

The present invention is a method for producing a new type of modified polyolefin to increase the compatibility of the non-polar polyolefin resin, more specifically, the low graft rate and high temperature conditions accompanying the production of the modified polyolefin by conventional extrusion method In order to overcome the disadvantage that it is difficult to remove excess functional monomers and to introduce various types of terminal functional groups, the polyolefin resin is dissolved using a solvent, and then the acid or acid anhydride is reacted in the presence of a reaction initiator to modify the modified polyolefin. After the preparation, it is reacted with a polyetheramine compound to produce a modified polyolefin.

Specifically, the method for producing the modified polyolefin of the present invention is characterized by including the following steps:

1) dissolving the polyolefin resin in an organic solvent;

2) reacting by injecting a radical reaction initiator into the polyolefin resin solution obtained in step 1);

3) injecting one or more dicarboxylic acids or acid anhydrides thereof into the solution obtained from step 2);

4) preparing a modified polyolefin precursor by injecting an unsaturated compound containing at least one unsaturated hydrocarbon functional group into the solution obtained in step 3) and reacting the same; And

5) reacting the modified polyolefin precursor obtained from step 4) with a polyetheramine compound to obtain a modified polyolefin.

The polyolefin resin that can be used in step 1) of the present invention is not particularly limited, but polyethylene and polypropylene are preferred, and the molecular weight used is 100,000 to 600,000 for polyethylene and polypropylene based on weight average molecular weight. 50,000-100,000 are preferable.

The organic solvent used in the step 1) is not particularly limited as long as it is a solvent capable of dissolving the polyolefin resin, for example, unsaturated hydrocarbons such as benzene, toluene, xylene, heptane, octane, nonane, Saturated hydrocarbons such as decane and halogenated organic solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene and trichloroethylene can be used, and bicyclic hydrocarbons and halogen-substituted hydrocarbon solvents are preferable, especially toluene, xylene and Chlorobenzene and the like can be suitably used. In addition, the aforementioned organic solvents may be used alone or in combination of two or more.

In the step 1), it is preferable to dissolve the polyolefin resin in the concentration of 100 ~ 400g / ℓ with respect to the organic solvent, if less than 100g / ℓ does not affect the reaction much, but there is a problem that the amount of solvent is increased is not preferable However, if the content exceeds 400 g / L, the viscosity of the solution at the time of reaction becomes high and the stirring is difficult, which is not preferable.

Step 2) is preferably carried out for 30 minutes to 6 hours at 85 ~ 200 ℃, preferably 90 ~ 150 ℃, so that the radical polymerization initiator can be sufficiently activated, and the polyolefin can be sufficiently dissolved, If the temperature is less than 85 ℃ or the dissolution time is less than 30 minutes, because the crystalline polyolefin is not sufficiently dissolved, activation by the radical initiator may not be sufficient, thus the graft rate is lowered, stirring due to an increase in the viscosity of the solution state If the temperature exceeds 200 ° C. or the dissolution time exceeds 6 hours, the crosslinking reaction may be promoted in the case of polyethylene due to overreaction with the reaction initiator, resulting in deterioration of processability. In the case of polypropylene, there is a problem of deteriorating resin properties due to the increase of low molecular weight. It is not.

In the step 2) of the present invention, the radical reaction initiator is preferably an organic peroxide, for example, benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexyn, di-t-butylperoxide, 1,3-bis (t-butylperoxy-isopropyl) benzene, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t -Butyl peroxy) hexane, t-butyl cumyl peroxide, t-butylperoxy-3,5,5-trimethylhexate, p-chlorobenzoyl peroxide, t-butyloxy benzoate, methyl ethyl ketone peroxide, Tris (t-butylperoxy) triazine, t-butylperoxy acetate, t-butylperoxy isoprocarbonate and the like.

It is preferable that content of the said radical reaction initiator is 3-15 weight part with respect to 100 weight part of polyolefin resin, and when it is less than 3 weight part, a graft rate falls and it is unpreferable, and when it exceeds 15 weight part, an excess radical reaction initiator It is not preferable because it results in the use of the resulting lowering of the physical properties due to the molecular weight decrease of the polyolefin, accompanied by side reactions with the reactants used.

The dicarboxylic acid or acid anhydride thereof used in step 3) is a radical reactive dicarboxylic acid or an acid anhydride thereof grafted to a polyolefin, and is not particularly limited in its kind, for example, maleic acid, phthalic acid, or eta. Cholic acid, citraconic acid, alkenylsuccinic acid, cis-1,2,3,6 tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydro phthalic acid or anhydrides thereof.

The dicarboxylic acid or an acid anhydride thereof is preferably 5 to 20 parts by weight based on 100 parts by weight of polyolefin resin, and less than 5 parts by weight, the graft ratio due to the lack of a reactant decreases, and is not preferable. Equation results in the use of excess dicarboxylic acid or acid anhydride thereof, which is undesirable due to the increase of unreacted materials and various side reactions.

The unsaturated compound containing at least one unsaturated hydrocarbon functional group used in the step 4) is an additive material for increasing the graft rate in the preparation of the modified polyolefin according to the present invention, and is not particularly limited in its kind, for example, styrene and divinyl. Compounds such as benzene, trivinylbenzene, allylbenzene, diallylbenzene, triallylbenzene, acrylamide, methacrylamide, diacrylate, triacrylate and triallyl isocyanurate can be used.

The amount of the unsaturated compound is preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin, but if outside the above range, the graft rate is lowered, or through the reaction with the polyolefin, individual polymerization or crosslinking is a side reaction. This is not desirable because it is likely to happen.

The modified polyolefin precursor obtained in step 4) is a modified polyolefin grafted with dicarboxylic acid or an acid anhydride thereof, and in order to react the modified polyolefin precursor with polyetheramine in step 5), a dissolution process is involved. In this case, as the solvent used, solvents that may be used when dissolving the polyolefin resin in step 1) may be used.

The polyetheramine used in step 5) is a compound necessary for carrying out the reaction with the dicarboxylic acid or its acid anhydride, wherein the polyetheramine is in the form of a monoamine, diamine, or triamine, and the backbone is polyoxidized. It is composed of ethylene or polypropylene oxide alone, or a combination of polyethylene and polypropylene oxide, and its weight molecular weight is 150 to 12,000, and polyetheramine having a weight molecular weight of 1000 to 3000 is more preferable.

The polyetheramine may be purchased from Huntsman, and specific examples thereof include monoamines such as Elastamine RE1-1000, RE1-2005, RE1-2007, RT-1000, RT-1400, Elastamine HE-150, HE-180, HE -1700, RE-600, RE-900, RE-2000 JEFFAMINE ED-6000, ED-4000, diamines such as ED-2003, ED-2001, D-2000 and D-4000, JEFFAMINE ET-3000, T- Triamines, such as 3000 and T-5000, etc. can be used.

The amount of the polyetheramine used is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the modified polyolefin precursor, and less than 5 parts by weight, the graft ratio due to the lack of reactants is lowered, which is not preferable, and exceeds 50 parts by weight. Is undesirable due to the increase of unreacted materials and various side reactions, resulting in the use of excess amine compounds.

In step 5), preferably, the reactant of the modified polyolefin precursor and polyetheramine is cooled to about 40 to 70 ° C., and then stirred in a solvent (eg, acetone) corresponding to 5 to 20 times the capacity of the total reaction system. It is added dropwise while washing, then filtered and dried to finally give a modified polyolefin resin.

The entire process of the modified polyolefin production method of the present invention as described above proceeds at normal pressure, thereby avoiding the complexity of the manufacturing process due to the pressurized state, there is an advantage that can promote the reaction more irreversibly.

The modified polyolefin obtained by the production method of the present invention has the following structure.

Wherein,

P: polyolefin chain,

R: hydrogen or a saturated or unsaturated hydrocarbon chain having 1 to 5 carbon atoms

E: A functional group having terminal groups as alkoxy and amine functional groups as a chain of ethylene oxide and / or propylene oxide derived from polyetheramine.

On the other hand, in each step of the production method of the present invention, the injection method for the dicarboxylic acid or an acid anhydride thereof, which is a reaction monomer grafted with the radical reaction initiator, and an unsaturated compound used as an additive for increasing the graft rate is particularly limited. Although not directly, or dissolved in the reaction solvent, the injection may be performed sequentially using a syringe pump.

According to the present invention, it is possible to easily produce a modified polyolefin having a high polar functional group having a variety of poly-oxide olefin skeleton, it is possible to provide a method for producing a modified polyolefin that can be produced by variously controlled graft content. This makes it easy to produce modified polyolefins that are well suited for blending with a wide variety of polymers, so that they can be easily applied to a variety of products through blends between polymers and polyolefins with polar functional groups, even with small amounts of modified polyolefins. It is expected to be very useful for the commercialization of various types of resins and polyolefins.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example  One

[denaturalization Polyolefin  Preparation of Precursor]

A 10 L sized autoreactor equipped with a stirrer, an oil heater, and a reflux condenser was sufficiently ventilated with nitrogen, 500 g of polypropylene was added thereto, 5 L of purified toluene was added thereto, followed by stirring for 1 hour while maintaining the temperature at 110 ° C. And completely dissolved. 15 g of benzoyl peroxide, 40 g of maleic anhydride, and 5 g of styrene were sequentially introduced into the completely dissolved polypropylene solution, and the reaction was terminated by refluxing at 110 ° C. for 4 hours. After the reaction was completed, the reaction system was slowly cooled to 60 ° C., and then the resultant modified polypropylene precursor was obtained by slowly adding dropwise to 40 L acetone solution. The resulting modified polypropylene precursor was filtered under reduced pressure, dried through a reduced pressure oven to complete the preparation, and the yield was 320 g. The functional monomer content contained in the resulting modified polypropylene precursor was used to make the sample into a sheet of 100 μm or less using a hot press, and then the peak intensity of the carbonyl group (1780 cm ⁻¹ ) of the FT-IR spectrum. (peak intensity) and area (area) were used to quantify. The graft content of the monomer was 7.5% by weight.

[denaturalization Polyolefin  Produce]

After fully ventilating a 1 L sized super-reactor equipped with a stirrer, an oil heater and a cooling reflux with nitrogen, 40 g of modified polypropylene precursor grafted with maleic anhydride prepared above and 400 ml of xylene were added thereto, and the stirring speed was 200 rpm. The temperature of the reactor was maintained at 130 ° C. during operation. After about 30 minutes, the modified polypropylene precursor was completely dissolved in the solvent. After 1 hour, 10 g of polyether monoamine (Elastamine RE1-1000, Huntsman's company) was slowly injected. When the injection was completed, the reactor was stirred for 4 hours while maintaining the temperature inside the reactor. After 4 hours when the reaction was completed, the reaction system was slowly cooled to 50 ~ 70 ℃ and slowly added dropwise to 4L acetone solution to obtain a modified polypropylene. The resulting modified polypropylene was filtered under reduced pressure and dried through a vacuum oven to complete the preparation. The yield was 39 g.

The presence and content of functional monomers in the resulting modified polypropylene were measured by FT-IR spectra. After the reaction, 1 g of the sample was taken and a specimen of 100 μm or less was prepared using a hot press, and then the FT-IR spectrum was measured to observe a change in the C═O band of the grafted functional monomer. acid anhydride) C = O bands of the byeonhwadoem was confirmed from 1780cm ^-1 to an imide of the C = O band of 1700cm ^-1. In addition, the quantification is polymer 2000, 41 . It was quantified from the calibration curve between the acid-base titration method of 1989 and the IR spectrum (C = O band area) of each representative sample. The reaction conversion rate in the final modified polyolefin production reaction is

% Conversion = [1-{(content of modified polyolefin precursor in synthesized modified polyolefin (g) / (content of modified polyolefin precursor (g)))}] * 100.

Example  2

[denaturalization Polyolefin  Produce]

Except for using 12g polyethermonoamine (Elastamine RE1-1000, Huntsman's) was prepared in the same manner as in Example 1, to obtain 38g of the resulting modified polypropylene.

Example  3

[denaturalization Polyolefin  Produce]

Except for using 15g of polyetherdiamine (JEFFAMINE ED-2003) in place of polyethermonoamine was prepared in the same manner as in Example 1, to obtain 42g of the resulting modified polypropylene.

Example  4

[denaturalization Polyolefin  Preparation of Precursor]

Except that 20g of divinylbenzene instead of styrene was prepared, and in the same manner as in Example 1, the resulting modified polypropylene precursor 320g was obtained, the graft content of the monomer was 15.2% by weight.

[denaturalization Polyolefin  Produce]

Prepared in the same manner as in Example 1 except for completely dissolving the modified polypropylene precursor at 150 ° C. using 400 ml of trichlorobenzene instead of xylene, and then adding 20 g of polyethermonoamine (Elastamine RE1-1000). To obtain 41 g of the resulting modified polypropylene.

Example  5

[denaturalization Polyolefin  Produce]

40 g of the modified polypropylene precursor was completely dissolved at 120 ° C. using 400 ml of xylene, and then prepared in the same manner as in Example 4, except that 25 g of polyethermonoamine (Elastamine RE1-2007) was added and reacted. 40 g of modified polypropylene was obtained.

Example  6

[denaturalization Polyolefin  Produce]

40 g of the modified polypropylene precursor was completely dissolved in 120 ml of xylene, and then prepared in the same manner as in Example 4, except that 17 g of polyetherdiamine (Elastamine HE-150) was added and reacted. 39 g of modified polypropylene was obtained.

Example  7

[denaturalization Polyolefin  Precursor preparation]

Except that 10g of styrene was prepared in the same manner as in Example 1, to obtain 330g of the resulting modified polypropylene precursor. The graft content of the monomer was 3.1% by weight.

[denaturalization Polyolefin  Produce]

The modified polypropylene precursor was completely dissolved at 130 ° C. using 400 ml of xylene, and was prepared in the same manner as in Example 1 except that 7 g of polyethermonoamine (Elastamine RE1-1000) was added. 38 g of propylene was obtained.

Example  8

[denaturalization Polyolefin  Produce]

40 g of the modified polypropylene precursor was completely dissolved at 120 ° C. using 400 ml of xylene, and was prepared in the same manner as in Example 7, except that 10 g of polyethermonoamine (Elastamine RE1-2007) was added. 42 g of polypropylene was obtained.

Example  9

[denaturalization Polyolefin  Produce]

40 g of the modified polypropylene precursor was completely dissolved at 120 ° C. using 400 ml of xylene, and then prepared in the same manner as in Example 1 except that 10 g of polyetherdiamine (JEFFAMINE ED-2003) was added. 40 g of polypropylene was obtained.

Comparative Example  One

[denaturalization Polyolefin  Precursor preparation]

After injecting 5 g of styrene into the completely dissolved polypropylene solution, 15 g of divinylbenzoyl peroxide and 40 g of maleic anhydride were sequentially injected, followed by refluxing at 110 ° C. for 4 hours to terminate the reaction. After the process was carried out in the same manner as in Example 1, to obtain 321 g of the resulting modified polypropylene precursor. The graft content of the monomer was 2.5% by weight.

[denaturalization Polyolefin  Produce]

The modified polypropylene precursor was completely dissolved at 130 ° C. using 400 ml of xylene, and was prepared in the same manner as in Example 1 except that 7 g of polyethermonoamine (Elastamine RE1-1000) was added. 39 g of propylene was obtained.

The graft ratios of the modified polyolefins obtained through Examples 1 to 9 and Comparative Example 1 are shown in Table 1 below. As shown in Table 1 below, when the unsaturated compound is injected and reacted before the reaction initiator and the dicarboxylic acid are injected, it can be seen that the graft rate is inferior to the method of the present invention.

Graft Rate of Precursor (wt%) Modified Polyolefin
Monomer (M) Graft Rate of Unreacted Precursors
(wt%) Conversion Rate (%) Example 1 7.5 Elastamine RE1-1000 0.15 98 Example 2 7.5 Elastamine RE1-2007 1.05 86 Example 3 7.5 Jaffamine ED-2003 1.58 79 Example 4 15.2 Elastamine RE1-1000 0.76 95 Example 5 15.2 Elastamine RE1-2007 3.50 77 Example 6 15.2 Elastamine HE-150 0.76 95 Example 7 3.1 Elastamine RE1-1000 0.22 93 Example 8 3.1 Elastamine RE1-2007 0.31 90 Example 9 3.1 Jaffamine ED-2003 0.53 83 Comparative Example 1 2.5 Elastamine RE1-1000 0.30 92

Claims (11)

A process for preparing a modified polyolefin, comprising the following steps:
1) dissolving the polyolefin resin in an organic solvent;
2) reacting by injecting a radical reaction initiator into the polyolefin resin solution obtained in step 1);
3) injecting one or more dicarboxylic acids or acid anhydrides thereof into the solution obtained from step 2);
4) preparing a modified polyolefin precursor by injecting an unsaturated compound containing at least one unsaturated hydrocarbon functional group into the solution obtained in step 3) and reacting the same; And
5) reacting the modified polyolefin precursor obtained from step 4) with a polyetheramine compound to obtain a modified polyolefin. The method of claim 1, wherein the polyolefin resin of step 1) is polyethylene or polypropylene. The method of claim 1, wherein the organic solvent is at least one member selected from the group consisting of saturated or unsaturated hydrocarbons and halogenated organic solvents. The method of claim 1, wherein in step 1), the polyolefin is dissolved at 100 to 400 g / l based on the organic solvent. The method of claim 1, wherein the radical reaction initiator of step 2) is an organic peroxide. The method of claim 1, wherein the radical reaction initiator in step 2) is used in 3 to 15 parts by weight based on 100 parts by weight of the polyolefin resin. According to claim 1, wherein the dicarboxylic acid or acid anhydride of step 3) is maleic acid, phthalic acid, itaconic acid, citraconic acid, cis-1,2,3,6 tetrahydrophthalic acid, 4-methyl-1, 2,3,6-tetrahydrophthalic acid and a method of producing a modified polyolefin, characterized in that selected from the group consisting of anhydrides thereof. The method of claim 1, wherein the dicarboxylic acid or an acid anhydride thereof is used in 5 to 20 parts by weight based on 100 parts by weight of the polyolefin resin. The method of claim 1, wherein the unsaturated compound of step 4) is styrene, divinylbenzene, trivinylbenzene, allylbenzene, diallylbenzene, triallylbenzene, acrylamide, methacrylamide, diacrylate, triacrylate and Method for producing a modified polyolefin, characterized in that selected from the group consisting of triallyl isocyanurate. The method of claim 1, wherein the polyetheramine compound of step 5) is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the modified polyolefin precursor. The method of claim 1, wherein the modified polyolefin prepared in step 5) has the following structural formula:

Wherein,
P: polyolefin chain,
R: hydrogen or a saturated or unsaturated hydrocarbon chain of 1 to 5 carbon atoms,
E: A functional group having an alkoxy and amine functional group as the end group.