JPS5884811A - Preparation of polyolefin graft modified material - Google Patents

Abstract

PURPOSE:To obtain the titled modified material under well maintained environmental conditions, by reacting a polyolefin with maleic anhydride and a polyol, kneading the resultant polyol ester of maleic anhydride with a radical generator under melting conditions, and extruding the resultant kneaded material. CONSTITUTION:A polyolefin, e.g. polyethylene, is mixed and reacted with maleic anhydride and a polyol, a low-molecular organic compound having two or more alcoholic groups in one molecule and no other functional group, e.g. ethylene glycol or glycerol, in portions, and finally with an equimolar amount or more of polyol at 50-200 deg.C for 10min-10hr to give (A) a polyol ester of maleic anhydride, which is then mixed with (B) a radical generator, e.g. dibutyl peroxide, and (C) a polyolefin stabilizer at 100-120 deg.C for about 10min-3hr. Thus, the grafting reaction is carried out while kneading and extruding the resultant mixture to give the aimed modified material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a modified polyolefin,
More specifically, the present invention relates to a method for producing a graft modified product by melt-kneading a polyol ester of maleic anhydride with a polyolein.

We are involved in the modification of polyolefins, including modification of catalysts, modification of copolymer compositions and copolymerization methods, and various additives, fillers, and other types of polyolefins. Modifications are carried out at the stage of polyoleain after polymerization, such as mixed groups of - or graft polymerization of other types of monomers. Gura Polymerization Jusha El! Methods in which the graft monomer to be used is treated with a radical initiator in polyolefin or other media or methods using radiation are also known, but neither has been put into widespread practical use. On the other hand, many attempts have been reported to modify polyolefins using graft monomers and radical generators at temperatures above the melting point of the polyolefin without using a solvent or medium. These include, for example, treatment of modified rubbery polyolefins for the purpose of internal crosslinking;
These include crosslinking of polyolefins, graft modification of polyolefins by addition of bi=-k%/mer, etc. One purpose of this graft modification is to improve the affinity of polyolefin with polar compounds, and for this purpose,
Maleic acid, acrylic #, etc. are considered to be the most preferred monomer for grafting. However, all of these monomers, ie vinyl monomers L, are volatile or sublimable.

Therefore, when trying to graft-modify polyolefin using these by the above-mentioned melting method, the volatilization of these volatile acids causes strong physiological irritation, which not only harms the working environment but also requires the ninth method to prevent irritation. Ventilation equipment for processing equipment,
A sealing device is required for handling,9 and volatile substances can cause trouble in the operation of the graft reactor, which does not interfere with the maintenance and maintenance of the reactor.

The present inventor has conducted intensive research to eliminate the environmental and maintenance disadvantages mentioned above when performing melt grafting as described above.As a result, even when improving the polarity of polyolefin, The present invention was completed based on the fact that by using a polyol ester of maleic anhydride in place of maleic acid, etc., the above-mentioned disadvantages were eliminated at once, and the grafting rate by melt grafting was also good. Ko0
The modified polyolefin obtained by 11K is used as an additive or base resin to improve affinity by blending with other resins, laminating, etc., and is also used as a mixing aid or base resin when distributing various materials. Used as a resin.

As is clear from the above description, an object of the present invention is to provide a method for producing a polyolefin without any environmental or maintenance disadvantages during the graft modification reaction. Another object is to provide a method for efficiently producing a polyolefin graft modified product having improved polarity. The present invention provides: (1) A method for producing a polyolefin graft modified product, which comprises cross-extruding a polyolefin, a polyol ester of maleic anhydride obtained by reacting toboliol maleic anhydride, and a radical generator in a molten state.

(2) The method according to item (1) above, wherein the polyol ester of maleic anhydride is obtained by reacting maleic anhydride with at least the same molar amount of polyol.

(3) React less than the equivalent mole of polyol with maleic anhydride, and then add an additional amount of primary polyol to the reaction product, such that the total amount with the initially used polyol is based on maleic anhydride. The method according to item (2) above, wherein the polyol is reacted in an amount equal to or more than the equivalent molar amount.

(4) The method according to item (1) above, in which the powdered polyolefin, polyol ester of maleic anhydride, and radical generator are mixed and then fed to an extruder.

(6) The rattan (with which the stabilizer for polyolefin is mixed)
4) Method.

The polyolefin used in the present invention includes polyethylene,
In addition to so-called olefin synthetic resins such as polypropylene, polybutene-1, and poly-4-methylpentene-1, EPR and EFT.

Also refers to so-called amorphous polymers such as polybutadiene.

The polyol ester of maleic anhydride used in the present invention is produced as follows. The polyol used is
- Any low-molecular organic compound that has two or more alcohol groups in its molecule and has no other functional groups, such as ethylene glycol, 1,1-propane, which has more than one primary alcohol group in one molecule Diol, l, 4-butanediol, 1,6-bentanediol, l.

11-ethane diol IiJ methylolethane.

Examples include trimethylolpropane, pentaerythritol, and dipentaerythritol. In addition, 1 in 1 molecule
-C, glycerin, which is a compound having both an alcohol group and a secondary or octane alcohol group.

1.2.6-Hexandriol, sorbitol, etc. As a matter of course, the reaction rate of primary alcohol groups with maleic anhydride is faster than that of secondary or octagonal alcohol groups, so in the present invention, this property of the polyol is used to minimize the amount of unreacted free maleic acid. use it to do.

The ratio of maleic anhydride to polyol is such that the amount of alcohol groups in the latter is equal to or greater than that of the former. A preferred quantitative ratio is, for example, 1 when the latter is a diol.
．． 0 to 1.5 and most preferably t'it, ot to 1,2. The reaction temperature is not limited, but is between 50°C and 200°C.
C Preferably, the reaction time is from 90° C. to 160° C. and the reaction time is from ViIO minutes to 10 hours, preferably from 80 minutes to 5 hours.It is also possible to react by mixing the same or different types of polyols in two or more stages. The method of segmental mixing of polyols together with the use of esterification catalysts is desirable because it allows for early reduction of free maleic anhydride in the reaction mixture. The polyol ester of maleic anhydride (hereinafter referred to as "-ester carboxylic acid") used in the present invention produced as described above is then mixed with a small amount of a radical generator in order to cause a graft reaction with a polyolefin, and then a predetermined amount of polyolefin is mixed with a small amount of a radical generator. Mix with powder and stabilizer for polyolefins.

Various known organic peroxides can be used as the above-mentioned radical generator. For example, dibutyl peroxide, dibutyl peroxide, dibutyl peroxide, bis(t-butyloxy)-padisopropylben, 2. Dialkyl-based compounds such as b-dimethyl-16-di(t-butylperoxy)hexane, etc. Idrono Kuichi Oxide.

hydroperoxides such as penzoylno(-oxide, rawaloyl peroxide, 1-butyl peracetate, t-butylno(-benzoate-cyclohexane peroxide, etc.), diacyl-based, ester-based and ketone-based non(-oxides), etc. .

The ratio of the radical generator to the ester carboxylic acid according to the present invention is 0.05 to 6% by weight, preferably 0.
．． 5~! ! %. It is also possible to use styrene in an amount up to a molar equivalent per a small amount of maleic acid as a radical generator. It is generally known that styrene is alternately copolymerized with maleic anhydride, but in the graft polymerization of ester carboxylic acid to polyolefin according to the present invention, it is important to note that the (anhydrous) maleic acid group in the ester carboxylic acid and styrene It is presumed that styrene is copolymerized alternately, and the coexistence of styrene is expected to contribute to improving the grafting rate of the polyolefin graft modified product of the present invention and to improving the physical properties of the modified polyolefin. 11i, the ester carboxylic acid formed when mixed with the polyolefin powder of @
Reduces the viscosity of the radical generator mixture and facilitates uniform mixing with the polyolefin powder.

The polyolefin powder polyolefin stabilizer, ester carboxylic acid, and radical generator are preferably prepared using a known blender, such as Henschel Mikina (trade name), before melting and blending, at room temperature or higher, preferably from 100"C to 1!O"C. Mix evenly. Since ester carboxylic acids are not necessarily liquid at room temperature, they may be softened or heated and mixed as a liquid, or they may be cooled and pulverized before use. The mixing time is not limited, but is 10 minutes to 3 hours, preferably 80 minutes to 3 hours. The mixing ratio is 10 parts of ester carboxylic acid (IK to 10 parts of polyolefin, preferably 1.6 to 6 parts of polyolefin)
), the polyolefin stabilizer is polyolefin species 1
11yo fio-511! & is. The mixing order is not limited, but for example, polyolefin first! 00~5GOof
After mixing 100 N noester carboxylic acid and 1-2 F radical generator, 1 kg to 6 of 9 polyolefin and 5-60 F stabilizer are mixed. The raw material mixture mixed as described above is then cross-extruded in an am state, during which a graft reaction is carried out. For this cross-wire extrusion, preferably a melt (cross-wire) extruder is used. From the viewpoint of the graft reaction, there is room for consideration of using other mixing machines or using a solvent method, but in the present invention, a two-wheel (multi-screw) mixing extruder is used as the extruder for molding. However, it is easier to implement than using other machines.

The conditions (temperature, residence time) for melt cross-mixing of the raw material mixture according to the present invention described above are specifically determined by the performance of the melt extruder used, but the conditions are such that cross-crossing is carried out smoothly and the radical initiator is In order for decomposition and graft polymerization to be carried out efficiently, the temperature of the molten part is 20°C to 50°C or higher than the melting point of the polyolefin used, and the residence time is 1 minute or more, preferably 8 minutes to 10 minutes. is necessary.

Since the graft reaction product of the present invention is a special ester carboxylic acid, in the case where maleic anhydride or a mono- or diester of maleic anhydride is graft-polymerized onto a polyolefin by melt mixing, Kll'pet; It has the feature of achieving high grafting efficiency in a short time (
(see Examples below), that is, the ester carboxylic acid 1
If even one of the many double bonds based on maleic anhydride in the molecule is grafted onto the polyolefin, the molecule can no longer be extracted with a solvent; Therefore, repeating melt extrusion of the raw material mixture according to the present invention also has the effect of increasing grafting efficiency.

The present invention will be explained below with reference to Examples.

Example 1. Control Example 1 Anhydrous Malay Y#98f (1.0 mol) and 46 g (0,848 mol) of trimethylolpropane were reacted at 180°C with stirring. After 8 hours, the maleic anhydride had almost completely reacted. 1.25 f of dicumyl peroxide was then added to the scissors reaction mixture and mixed to produce the ester carboxylic acid reaction product of the present invention for use in subsequent steps.

60f (D) The reaction product and 2001 polypropylene powder were mixed for 80 minutes at 110'C to 130°C in a high speed mixer, then 1.8# polypropylene powder and 5f mixed stabilizer (Note: Stabilizer composition for polypropylene) was added and mixed for 3 minutes at the same temperature.In the above mixing process, an ester carboxylic acid reaction product obtained by reacting maleic anhydride and polyol in advance was used. On the other hand, the ester carboxylic acid reaction product obtained as described above had a high viscosity and required careful mixing.
0ff Supply to extruder, cylinder temperature 80℃~28
The extruded strands were cut into pellets at a die temperature of 0°C and 180″C. The resulting pellets were cooled with dry ice acetone, and the cooled pellets were ground with a high-speed grinder to form fine powder. .

Then, the main powder of 201 was placed in a Soxhlet extractor and extracted with acetone for 72 hours. A comparative example 1 was prepared in the same manner as in Example 1 except that the ester carboxylic acid reaction product was not mixed (mixing, mixing, cutting, pulverization, and extraction).

The amount extracted by acetone extraction in Example 1 was 0 or more after correcting the mixed stabilizer and other extracts according to the extraction amount in Lighting Example 1. Therefore, what is the ratio of non-extractable ester carboxylic acid graft-polymerized to polypropylene? ! It was 6%. Separately, a sheet was obtained by hot pressing using the material to be extracted (graft-polymerized polypropylene), the infrared absorption of this sheet was measured, and the malein content was determined from the intensity of the C The amount of acid bound is 1.49%.

Comparative Example-t, 2 The same procedure as Example 81 was carried out except that dicumyl peroxide was not mixed. The amount of ester carboxylic acid obtained by acetone extraction was 5.5% per 2Of - the proportion of non-extractable ester carboxylic acid was 5.5%, and the amount of maleic am in the press sheet by infrared absorption was 0.15% (Comparative Example 1 ).

In addition, the same procedure was carried out except that maleic anhydride 989 was used in place of the ester carboxylic acid reaction product (Comparative Example 2).
). In this case, the working environment was not only severely stimulated by the sublimation of maleic anhydride during mixing in the high-speed mixer and pelletizing, but also the maleic anhydride caused severe clogging at the extruder vent. In addition, no minute infrared absorption due to maleic acid was observed in the sheet produced from the acetone extract after pulverizing the pellets.
It was found that the grafting reaction of maleic anhydride to polypropylene did not occur in mixed-wire pelletization with the addition of maleic anhydride. When a radical additive was added at the same time, the graft reaction proceeded, but the stimulation of maleic anhydride could not be avoided.

Actual feeding, control example 2 Maleic anhydride 11af (1.0 mol) and pentaerythritol 11@tc0.264 mol) were mixed at 116"C
The mixture was reacted for 6 hours with stirring. For the reaction mixture, b-
Dimethyl-2,6-ditertiary-butylperoxyhexane tt was added, mixed, and then cooled to room temperature to produce an ester carboxylic acid reaction product for graft polymerization as a viscous solid carbonate. Goyo Mukuro reaction main reaction product 010 polyppyrene powder was heated at 110°C to tWO in a high speed construction mixer.
After assembling with SO for minutes at ℃, add 11l of FO polybupylene powder and 6f of mixing stabilizer and mix for 8 minutes at the same temperature. In comparison, I didn't feel the stinging smell at all. Then, the obtained well-formed product was fed to a 20WM extruder, and the cylinder temperature was 111"C~!
Extrusion recycling was performed at a die temperature of 00°C and 180°C, and the resulting strands were cut into pellets. The obtained pellets were cooled, pulverized, and extracted with acetone in the same manner as in Example 1. A control example 2 was prepared in the same manner as in Example 2 except that the ester carboxylic acid was not mixed (mixing, mixing, cutting, pulverization, and extraction).

The amount of acetone extraction in Example 2 (carried out 8 times, average value) was corrected for the mixed stabilizer and other extracts based on the amount of extraction in Control Example 2. The method of acetone extraction was carried out in the same manner as in Example 1. As a result, the 8-time average value of the amount of extract was 0.186F, and the ratio of the extract to the added ester carboxylic acid was 28.8%. Therefore, the remaining ratio, that is, the ratio of the ester carboxylic acid grafted to polypropylene was It was 76.7%. Separately, a sheet was obtained by hot pressing using the extractable material (graft-polymerized polypropylene), and the infrared absorption of this sheet was measured. The binding amount is 1.60%.

Example 8 Maleic anhydride 98f (1.0 mol) was reacted with 1,6-hexane diol 61f (0.51 mol, 8% excess from the calculated amount) under stirring in tso'c. After 2 hours of reaction, 115f of 2,6-dimethyl-16-di(tert. 9. Produce carvone reaction product).

8Oft) wrinkle ester carginic acid reaction product and! OOf
of propylene ethylene copolymer (MFR 6.0, containing 8.5% ethylene) powder in a high speed mixer at 110%
1.8# of the same copolymer after mixing for 16 minutes at ~180°C.
Add q-powder and 5F mixed stabilizer for polypropylene and mix for 6 minutes at the same temperature. Even in the above mixing step and the next step of charging the resulting mixture into an extruder, there was no physiological stimulation caused by maleic acid with respect to the mixture. The resulting mixture was then kept at a die temperature of ~280°C [
Pellets were obtained by cutting the extruded strands at 180° C. with an average residence time of 2 minutes. The obtained pellets were cooled, finely pulverized, and extracted with acetone in the same manner as in Example 1, and the average value of the amount of crest extracted was calculated eight times, and the amount of stabilizer added was subtracted from the extracted amount. #) was calculated. The above results, Example-1
The extracted ester carboxylic acid cap by acetone extraction was 0.2811 (extraction rate 48.4%), so the grafting efficiency was 61.6%. On the other hand, the maleic acid content determined by carbonyl content #1 in the press sheet by infrared absorption (IR method) using the extraction residue (graft copolymer) was 0.9θ%.

Example 4 Trimethylolpropane 46F (0,848 mol) in an equivalent molar excess of anhydrous polymer 1298F (1,0 mol) was mixed, heated and melted at 110 to 180"C, and reacted with stirring. After 8 hours of reaction, the reaction mixture was cooled to 80°C, and styrene Uf (0.60 mol) was added to the resulting solution. 0.6 f of hexane was added and mixed, and the ester carboxylic acid styrene mixture [8 (1) was used to perform the graft reaction in the next step and subsequent steps.

That is, the @OfO ester carboxylic acid styrene mixture, 2# polypropylene powder, and 54 mixed stabilizer were mixed in a high-speed mixer at 110° C. for 10 minutes. Then, the obtained mixture was fed to a 20ff extruder, and the cylinder temperature was 180°C~! The extruded strand was cut into pellets at a die temperature of 30°C [180°C and an average residence time of 2 minutes]. In each of the above reaction, mixing and extrusion steps 11, there is no physiological stimulation caused by maleic anhydride. Next, the pellets were extracted with acetone in the same manner as in Example 1.

The grafting rate of the extracted material was 64%. On the other hand, the maleic acid content determined by infrared absorption of a 9-press sheet made in the same manner as in Example 1 was 1.65%.

Run 915 Anhydrous Maleia 1 m98 f (1,0 mol) Topenta x
- #20 f (0.15 mol) t 1
The mixture was heated at 10° C. to 180° C. with stirring to mix and dissolve pentaerythritol. 1 more in wI mixed lysate
, 4-buta/diol 18F (0.2 mol) was added and mixed, reacted at 180'C for 8 hours, and left to cool, the reaction mixture turned into a solid (ester carboxylic acid). 'The wrinkled solid was placed in tetracyclic carbon and cooled by adding dry ice. The cooled solid was then ground in a high speed pulverizer. # The pulverized product was dried under reduced pressure (5 #Hg) at 25° C. for 12 hours to obtain ester carboxylic acid fine powder to be used in the subsequent grafting reaction. The above fine powder of No. 601, polypropylene powder of No. 9, 0.5 f of bis-(t-butylperoxy) inglobilbenzene and 51 F of synthetic stabilizer were mixed in a high-speed mixer at 110°C for 5 oz.
Mixed for a minute. The resulting mixture was then fed into a 20111 extruder and extruded at a cylinder temperature of 180-210°C and a die temperature of 180°C to cut nine strands into pellets. The efficiency of the grafting reaction was determined from the extraction rate by treating the pellets obtained in the same manner as in Example 1, and found that the efficiency of the grafting reaction was 62%.

Example 8 Maleic anhydride 59298F (1.0 mol) and dipentaerythritol 20f (0,084 mol, 0.5 mol commercial amount) were mixed together with 0.2 f of tin octylate as a reaction catalyst.
A heating dissolution reaction was carried out at 80°C for 2 hours with stirring. Then 1,4-butanediol 26 f (0,
Add 28 mol and another 0.56 mol, dissolve and react at the same temperature for 8 hours. Thereafter, the mixture was cooled to room temperature and left to solidify as a whole. Next, the solidified product was cooled in carbon tetrachloride dry ice and treated with a high-speed pulverizer, and the resulting fine powder was heated at room temperature under reduced pressure (5 sw) for 12 hours.
Hg) to obtain ester carboxylic acid fine powder to be used in the subsequent grafting reaction. Except for using the above-mentioned fine powder of 60 f, the same procedure as in Example 1 was carried out, such as cooling and pulverization of the let in a high-speed mixer, extraction of the pulverized product with acetone, and calculation of the grafting ratio. As a result, the crafting rate was 77%
Met. The maleic acid content of the press sheet obtained in the same manner as in Example 5, determined by infrared absorption measurement, was 1.55.
%Met.

that's all Patent applicant: Kumamoto Institute of Technology Chisso Corporation

Claims (8)

[Claims] (1) A method for producing a polyolefin graft modified product, which comprises kneading and extruding a polyolefin, a polyol ester of maleic anhydride obtained by reacting maleic anhydride with a polyol, and a radical generator in a molten state. (2) The method according to claim (1), wherein the polyol ester of i-leic anhydride is obtained by reacting maleic anhydride with at least the same molar amount of polyol. (3) React less than the equivalent mole of polyol with maleic anhydride, and then add an additional amount of primary polyol to the reaction product, such that the total amount with the initially used polyol is based on maleic anhydride. The method according to claim 2, wherein the polyol is reacted in an amount of at least 100 molar. (4) The method according to claim (1), in which the powdered polyolefin, polyol ester of maleic anhydride, and radical generator are mixed and then fed into an extruder. (5) The method according to claim (4), in which a stabilizer for polyolefin is mixed. (6) Ho'J Allka, Ethylene Glycol l118-
Propanediol, 1.4-butanediol, 1.5-
Claim No. (1) which is bentanediol, 1,6-hexanediol or neopentyl glycodog.
Section method. (7) The polyol is glycerin, 1,2,6-hexanediol, or trimethylolethane. The method of claim (1), wherein the trimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol is used. (8) The radical initiator is dibutyl peroxide, dicumyl peroxide, ad bis(1-butylperoxy)-halinepropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, t
-butylno-hydropero dP side, cumyl hydroperoxide, paramenthane hydroperoxide. Pennzoyl peroxide medium side, Tsukuroyil peroxide. Claim (1) The method of JJ, which is t-butyl peracetate, t-butyl perbenzoate, or cyclohexynyl oxide.