CN1240456A - Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto - Google Patents
Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto Download PDFInfo
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- CN1240456A CN1240456A CN 97180618 CN97180618A CN1240456A CN 1240456 A CN1240456 A CN 1240456A CN 97180618 CN97180618 CN 97180618 CN 97180618 A CN97180618 A CN 97180618A CN 1240456 A CN1240456 A CN 1240456A
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Abstract
A polyolefin, such as polyethylene or polypropylene, is modified by grafting onto the polyolefin backbone from 5 weight percent to about 30 weight percent of 2-hydroxyethyl methacrylate. Suitable polyethylene compositions for grafting include ultra high molecular weight polyethylene, high density polyethylene, ultra low density polyethylene, low density polyethylene, linear low density polyethylene and polypropylene.
Description
Background of the present invention
The present invention relates to graft copolymer of polyolefine and alkyl acrylate and preparation method thereof.More particularly, the present invention relates to methacrylic acid 2-hydroxyl ethyl ester fusion-grafting on polyethylene and acrylic resin and relate to the method for preparing this base polymer.
Polyolefine such as polyethylene and polypropylene are non-polar polymers, its general repeller part.These polyolefine usually commercial as the purposes aspect the barrier film.This class purposes comprises the wrapping material that resemble commodity such as health napkin, diaper, adult's paper nappy such as disposable personal belongings.
The exhausted polymkeric substance is generally handled by recirculation, burning or sanitary landfill.Because be sent to the increase of the amount of sanitary landfill, its for non-biodegradable material, can not compost material or can not biological degradation can not compost material become even more important.In disposable personal belongings field, the polyethylene film layer of outside must be separated with remaining absorbent structures or the entire structure thing must be pulverized.
Ten years in the past, people for existing polymer modification to obtain the having character of improvement and to be that the interest of industrial important multipolymer of special property is more and more denseer sometimes.Be apparent that especially all the time and try hard to use polar functional monomer such as vinylformic acid and the ester modified commercial polymer of acrylic acid alkyl such as polyolefine.For example, form the multipolymer as tack coat of coextrusion character up to the t-butylaminoethyl methacrylate (t-BAEMA) of about 5% (weight) by fusion-grafting, with the linear low density polyethylene modification with improvement.These tack coats satisfy particular requirement and are that the packing of Administrative Regulations is important sometimes for producing economically in packaging industry and film industry.
Also used the corresponding esters modified polyolefin of acrylate such as methyl acrylate, vinylformic acid 2-butyl ester, 2-EHA, decyl acrylate, octadecyl acrylate and methacrylic acid.
In addition, concerning plastics, more and more pay attention to the environment for use safety dope.These coating are reducing and rely on polarity coating such as water material on the use of solvent-based coating and the increasing degree.The effectiveness of graft copolymer of the present invention is including, but not limited to the material that polarity coating is had big affinity.Other purposes can comprise wire coating, injection molded article and barrier film, has the mechanical miscibility of raising between graft copolymer of the present invention and hydrophilic composition.
The production of described composition is generally all finished by all components being admixed in the monomeric resin compound of coating all the time.To in the presence of a kind of reaction initiator, push with the multiphase mixture of monomer coating resin then and form a kind of graft copolymer.This method has been successfully used to produce the graft copolymer with low grafted monomer weight percentage.But this method is low with monomer-grafted efficient to polyolefin resin, less than 50%.Because the poor efficiency of the limited and method of grafting, have the monomeric graft copolymer of greater amount that had on polyolefine grafting and can prepare the needs of the effective ways of this analog copolymer.
Overview of the present invention
In brief, the present invention has the polyolefine of 95-about 70% (weight) and the rest part of its composition is the modified polyolefin multipolymer of grafted alkyl acrylate monomer thereon, and wherein the per-cent of grafted monomer is based on the weight of described polyolefine and grafting (methyl) acrylate.More particularly, composition of the present invention is a kind of have about 95-70% (weight) polyolefine and about 5-30% (weight) ethene of grafted methacrylic acid 2-hydroxyl ethyl ester (HEMA) or composition of propene polymer thereon.Methacrylic acid 2-hydroxyl ethyl ester described in this and HEMA are with a kind of compound.
Find unexpectedly that now polyethylene or polyacrylic graft copolymer can obtain by the methacrylic acid 2-hydroxyl ethyl ester fusion-grafting with high level (about 30% (weight) of 5-) to described polyolefin backbone.
Another aspect of the present invention is the method for preparing the graft copolymer described in this.Polyolefin copolymer of the present invention can prepare by the following method: under the fusion-grafting condition, in the reactor that is fit to, add predetermined amount polyolefin polymer, and in this melts the methacrylic acid 2-hydroxyl ethyl ester monomer of adding predetermined amount and capacity reaction initiator and the methacrylic acid 2-hydroxyl ethyl ester of about 30% (weight) of 5-is grafted on the polyolefine.The polyolefin copolymer that forms needs enough coolings so that melts solidifies.
Main purpose of the present invention has provided on polyolefine grafting and has had a composition than the grafted monomer of the higher weight percent of previously known method.The present invention is the target above monomeric graft copolymer polyolefine of 5% (weight) that provided grafting thereon more specifically.
Another target of the present invention provides the composition of the methacrylic acid of the grafted thereon 2-hydroxyl ethyl ester with about 70% (weight) polyethylene of 95-and about 30% (weight) of 5-.
Another target of the present invention provides the composition of the methacrylic acid of the grafted thereon 2-hydroxyl ethyl ester with about 70% (weight) polypropylene of 95-and about 30% (weight) of 5-.
Also target of the present invention provides under melting condition the method for methacrylic acid 2-hydroxyl ethyl ester fusion-grafting to the polyolefin resin.
Detailed description of the present invention
The unsaturated ethylene polymkeric substance that is used for enforcement of the present invention is that homopolymer or ethene and polyacrylic multipolymer and structure are essentially linear.Used term " saturated " is meant complete saturated polymkeric substance in this, but also comprises the polymkeric substance that contains maximum about 5% degrees of unsaturation.The homopolymer of described ethene comprises that the homopolymer for preparing under the low pressure is linea low density or high density polyethylene(HDPE), or the homopolymer that high pressure prepares down is branch or new LDPE (film grade).The general feature of high density polyethylene(HDPE) is that its density approximates or restrains (g/cc) greater than every cubic centimetre 0.94.In general, has the density of the about 0.97g/cc of about 0.94-as the high density polyethylene(HDPE) of base resin in the present invention.Described polyethylene can have about 0.005-100 and divide Grams Per Minute (dg/min) at 2.16kg and 190 ℃ of melt indexs of measuring down.Described polyethylene preferably has the melt index of the about 50dg/min of 0.01-, more preferably has the melt index of the about 25dg/min of 0.05-.Perhaps, also can use polyethylene mixture as the base resin in the described graft copolymer composition of preparation, this class mixture can have greater than 0.005 to the melt index less than about 100dg/min.
Described new LDPE (film grade) has less than 0.94g/cc and is generally the density of the about 0.93g/cc of 0.91-.Described low density polyethylene polymer has the melt index of the about 100dg/min of about 0.05-, the preferred about 20dg/min of 0.05-.Can use ultra-low density polyethylene according to the present invention.In general ultra-low density polyethylene has the following density of 0.90g/cc.
In general, polypropylene has a kind of semi-crystalline structure, has about 40000 or the fusing point of the density of above molecular weight, about 0.90g/cc, 168-171 ℃ and the tensile strength of 5000psi for isotactic polypropylene.Polypropylene also can have other tacticity such as syndiotaxy and random.
Can be used for the multipolymer that ethylene copolymer among the present invention can comprise ethene and one or more other polymerizables, unsaturated monomer.The example of this analog copolymer includes but not limited to: comprise the ethene of linear low density polyethylene and the multipolymer of alhpa olefin (such as propylene, butylene, hexene or octene); Ethene and linearity or ramose have the multipolymer of vinyl ester of carboxylic acid of 1-24 carbon atom such as vinyl-vinyl acetate copolymer; With the multipolymer of ethene with the acrylic or methacrylic acid esters of linearity, branch or closed chain alkanol with 1-28 carbon atom.The example of aftermentioned multipolymer comprises that ethene-(methyl) alkyl acrylate copolymer is such as ethylene-methyl acrylate copolymer.
The radical initiator that can be used in the invention process comprises that acyl peroxide is such as benzoyl peroxide; Dialkyl group, diaryl or aromatic alkyl superoxide such as di-t-butyl peroxide, dicumyl peroxide, peroxidation cumyl butyl, 1,1-di-t-butyl peroxide-3,5,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexin-3 and two (a-t-butyl peroxy isopropyl benzene); Peroxyester such as t-butylperoxy pivarate, cross the sad tert-butyl ester, t-butylperoxyl benzoate, 2,5-dimethyl hexyl-2, is crossed a dialkyl carbonate and is crossed two dialkyl carbonates 5-two (perbenzoate), two (crossing the O-phthalic tert-butyl acrylate); Hydroperoxide such as t-butyl peroxy hydrogen, p-methane hydroperoxy-, pinane hydroperoxy-and cumene hydroperoxide and ketone peroxide such as cyclohexanone peroxide and methylethyl ketone peroxide.Also can use azo-compound such as Diisopropyl azodicarboxylate.
Other can join in the described graft copolymer performance with further enhancing product for the known component of those skilled in the art.For example can add polyoxyethylene glycol to improve melt viscosity.Also can sneak into other additive types of just being usually used in the polymer blend so that required characteristic to be provided, for example static inhibitor, pigment, tinting material etc.In addition, processing property can be improved by lubricant or surface slip agent are blended in the described blend.The consumption of all these additives is all less, is less than 3% (weight) usually.
Another aspect of the present invention is the method for the described compound of preparation.In general, in low grafting level (monomer is less than 3% (weight) usually), method therefor is crucial especially, can be undertaken by before refining of melt roller or grafting the polyolefine of required weight ratio and methacrylic acid 2-hydroxyl ethyl ester being mixed in mixing device altogether.When the grafting more than 3%, being blended in the above temperature of softening temperature or carrying out being higher than the distortion of described raw material experience and becoming under the temperature of molten state or fluid attitude of methacrylic acid 2-hydroxyl ethyl ester and polyolefin polymer.
The mechanical deformation in a suitable mixing device with polyolefine and methacrylic acid 2-hydroxyl ethyl ester, the example of described mixing device comprise that mine-laying Bender degree of moulding registering instrument, roller refining machine, single screw rod or multiscrew extrusion machine or any other are the known mechanical mixing equipment that is usually used in mixing, compounding, processing or the secondary processing of polymkeric substance of those skilled in the art.A kind of required especially reactor is to have one or more mouthfuls extrusion machine.
Solid polyolefin such as pellet or powder can join in the mixing device simultaneously with methacrylic acid 2-hydroxyl ethyl ester and initiator.Optional, if mixing device has more than one mouthful, methacrylic acid 2-hydroxyl ethyl ester and initiator component can be added in the fused polyolefin polymkeric substance.
In the method for the invention, to load in mixture the feeding rate of putting be important to each component toward molten.But methacrylic acid 2-hydroxyl ethyl ester and initiator continuous measurement join in the extrusion machine or a time cycle and divide several sections to add to impel the evenly grafting in whole polyolefin polymer material of described monomer.Although do not wish to be bound by any theory, it is generally acknowledged that described reaction is exceedingly fast and when methacrylic acid 2-hydroxyl ethyl ester contacts with the fused polyolefin polymkeric substance with initiator reaction just big portion finish.Yet although molten polymer just moves away from the point of contact of beginning, described reaction may still continue.Radical initiator should be delivered in the fusing blend with the corresponding speed of methacrylic acid 2-hydroxyl ethyl ester feeding rate with one, the ratio that is initiator raw material (weight meter) and raw material monomer (weight meter) is greater than about 0.025, the preferred relative feeding rate of radical initiator is about 0.025-about 0.1, more preferably about 0.025-is about 0.075, and most preferably is about 0.0375-about 0.06.
Methacrylic acid 2-hydroxyl ethyl ester monomer may join in the described fusing blend with the corresponding speed of polyolefine feeding rate with one, be monomer (weight meter) and the ratio of polyolefine (weight meter) is that 0.05-is about 0.3, the relative feeding rate of preferred monomers is about 0.25 for about 0.1-, about 0.1-about 0.2 more preferably.Now find unexpectedly by adding radical initiator and methacrylic acid 2-hydroxyl ethyl ester with above-mentioned ratio, with a certain amount of monomer-grafted efficient to polyolefine greater than about 50%.
Described extrusion machine can have more than one for the mouth that adds polyolefin polymer, has one or more for the injection port that adds methacrylic acid 2-hydroxyl ethyl ester and/or initiator in the fused polyolefin part.Described extrusion machine also can have a volatile matter that has the part of depressor area for any unreacted methacrylic acid 2-hydroxyl ethyl ester of discharging and/or formation in treating processes.
The grafting methacrylic acid 2-hydroxyl ethyl ester content of final modified polyolefin polymkeric substance can from based on 5% (weight) of monomer of sending into and polyolefin resin total amount to about 30% (weight).At described polyolefine is that the grafted amount is necessary to reach 10% (weight) to about 25% (weight) on polyethylene or the polypropylene, more preferably reaches about 10-20% (weight).
Although above-mentioned each scope has been stated occurrence, it will be understood by those skilled in the art that this scope is included in all values in those scopes that specifically do not indicate this value herein undoubtedly.
The present invention will illustrate in greater detail by following specific embodiment, but is to be understood that they are illustrative embodiment, and the present invention is not subjected to the restriction of any its described details, and should be interpreted as expressly in scope and spirit of the present invention.
For embodiment 1-13, every type polyethylene is obtained a linear regression calibration curve according to following method.
Synthesizing of poly-(methacrylic acid 2-hydroxyl ethyl ester) homopolymer
520g ethyl acetate and 130g methacrylic acid 2-hydroxyl ethyl ester are joined in 1 liter of three-necked flask.Under agitation flask is heated to 60-65 ℃.Close described system and use nitrogen purge 1 hour.Open system and the 1.12g benzoyl peroxide is joined in described ethyl acetate/methacrylic acid 2-hydroxyl ethyl ester solution.Closure systems and use nitrogen purge once more.After about 4 hours, formed a kind of white precipitate.With white depositions from flask shift out, suction strainer is removed unnecessary solvent and with the washing of 100-200ml ethyl acetate.With this white depositions in the vacuum chamber of 50 ℃ and 26 inches Hg posts dry 10 hours to remove all solvents.
Obtain measuring the calibration curve of grafting percentage level by the fourier infrared analysis
The polyethylene of predetermined weight ratio and the sample of institute's synthetic poly-(methacrylic acid 2-hydroxyl ethyl ester) are melted blend in the mixed device at one.The compression moulding under the pressure of 374 temperature and 10000-20000psi of the film of these known blend compositions.For each polyethylene/poly-(methacrylic acid 2-hydroxyl ethyl ester) blend, use fourier infrared to be determined at 1725cm
-1(because the carbonyl on methacrylic acid 2-hydroxyl ethyl ester) located and 720cm
-1(because polyethylene) locates the peak height ratio of absorption band.Use this data, make 1725cm
-1With 720cm
-1Peak height ratios to the figure of poly-(methacrylic acid 2-hydroxyl ethyl ester) percentage composition in the described blend.Use linear regression, by the described data the suitableeest fit line that draws.
The suitableeest match equation of linear regression of new LDPE (film grade) is:
% grafted HEMA=3.82+65.05 (1725cm
-1With 720cm
-1Ratio)
The suitableeest match equation of linear regression of linear low density polyethylene is:
% grafted HEMA=-0.38+38.63 (1725cm
-1With 720cm
-1Ratio)
Embodiment 1-4
By reactive extrusion with a kind of low density polyethylene polymer with 1.9dg/min melt index (can be available from Dow Chemical Company, Midland is MI) with the grafting of methacrylic acid 2-hydroxyl ethyl ester.This is a single step continuation method, and wherein said graft reaction is at 30 millimeters twin-screw extruder (Werner ﹠amp of a tool vacuum devolatilization; Pfleiderer carries out in ZSK-30).Described extrusion machine has total operation length of 880 millimeters, nine barrel sections and five heating zone.No. 1 machine barrel water cooling.Machine barrel 2 and 3 heating unit are synthesized 1 district, machine barrel 4 and 5 and are synthesized that 2 districts, machine barrel 6 and 7 are synthesized 3 districts, machine barrel 9 is that 4 districts and die head are 5 districts.The vacuum devolatilization carries out beginning to locate about 700 millimeters places from screw rod.Described polyvinyl resin feeding rate is 22 pounds/hour, and the monomeric feeding rate of described methacrylic acid 2-hydroxyl ethyl ester is 2.2 pounds/hour, and the feeding rate of radical initiator is shown in following table 1 separately.The constitutive material that adds extrusion machine is included in ldpe resin that the charging trunnion of extrusion machine adds simultaneously, methacrylic acid 2-hydroxyl ethyl ester monomer solution (can be available from Aldrich Chemical Company, Milwaukee, Wisconsin) and initiator 2,5-dimethyl-2, (supplier is elf Atochem to 5-two (t-butyl peroxy) hexane, 2000Market St., Philadelphia, PA 19103-3222, commodity are called Lupersol101).The helix speed of described extrusion machine is 300 rev/mins.Described polymer melt is squeezed into wire rod and cools off in water-bath, subsequently by strand pelletizing mechanism grain.The material grain collected was anhydrated to remove down in vacuum (29 inches Hg) in dry 18 hours.
The purifying modified polyolefin is for measuring grafting HEMA content
In order to remove the homopolymer of unreacted methacrylic acid 2-hydroxyl ethyl ester and any methacrylic acid 2-hydroxyl ethyl ester, with the reaction product purifying.The modified polyolefin product that 5 grams are obtained in described embodiment joins in the round-bottomed flask that contains 125 milliliters of dimethylbenzene to carry out the purifying of modified polyolefin.Flask is mixed a condenser and passed through magnetic stirrer.In oil bath, content is heated to 140-150 ℃ and refluxed 2 hours.After treating that modified polyolefin is dissolved in the described solution fully, hot xylene solution is joined under continue stirring at room temperature the beaker that contains 800 milliliters of acetone.Collect the throw out of purifying also with 100 milliliters of washing with acetones by vacuum filtration.Purified throw out is dry up to removing all solvents in the vacuum chamber of 50 ℃ and 25-30 inch Hg.
Purified product is depressed to film and uses fourier transform infrared spectrometer (FT-IR) analysis with 10000-20000psi at 374 °F.(5225 Verona Road, P.O.Box 44451, Madison, the Impact 400 type infrared spectrometers of WI53744-4451) producing collection FT-IR spectrogram with a Nicolet InstrumentCorporation.In order to measure the graft(ing) degree of methacrylic acid 2-hydroxyl ethyl ester on concrete polyethylene on the concrete squeezing prod, each purified product is determined at 1725cm
-1(because on methacrylic acid 2-hydroxyl ethyl ester carbonyl) locate bands of a spectrum with at 720cm
-1(because polyethylene) locates the peak height ratios of bands of a spectrum.Above-mentioned calibration curve equation is used to described peak height ratios is changed into the weight percent of grafted methacrylic acid 2-hydroxyl ethyl ester in each sample.Grafting level and grafting efficiency the results are shown in the following table 1.Described per-cent is based on the weight percent of polyethylene and grafted methacrylic acid 2-hydroxyl ethyl ester weight.About the comprehensive discussion that uses FT-IR mensuration grafting efficiency can be referring to " the Meltgrafting of t-butylaminoethyl methacrylate on polyethylene " of Song that incorporates this paper by reference into and Baker, POLYMER, 33 volumes, 15 phases (1992).
Table 1
Embodiment 5-13
| Embodiment | District's temperature, ℃ | Initiator speed Pounds Per Hour | FT-IR ratio | Percentage of grafting % | Grafting efficiency % |
| 1 | 159，175，183， 173，181 | ?0.022 | ?0.0188 | ?5.0 | ?50 |
| 2 | 160，180，187， 177，181 | ?0.044 | ?0.0438 | ?6.6 | ?66 |
| 3 | 161，180，188， 178，181 | ?0.066 | ?0.0770 | ?8.7 | ?87 |
| 4 | 166，180，189， 178，181 | ?0.088 | ?0.0561 | ?7.3 | ?73 |
For embodiment 5-13, with the linear low density polyethylene of the density of a kind of melt index with 1.9dg/min and 0.917g/cc (by Dow Chemical Company, Midland, MI provides) delivering to a Haake twin-screw extruder (can be available from Haake, 53West Century Road, Paramus, NJ, 07652) in.Described extrusion machine 300 millimeters long have backwards rotation biconical screw rod.Each conical screw is 30 millimeters at opening for feed, is 20 millimeters at die head.Extrusion machine has 4 humidity provinces, and die head is decided to be the 4th district.The temperature in each district is as shown in table 2.The constitutive material that adds extrusion machine is included in 5 Pounds Per Hours the linear low density polyethylene resin that the charging trunnion of extrusion machine adds simultaneously, and the feeding rate of the methacrylic acid 2-hydroxyl ethyl ester of each embodiment and initiator (Lupersol 101) is:
Embodiment 5: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.25 Pounds Per Hour, and the feeding rate of initiator is 0.017 Pounds Per Hour, and screw speed is 150 rev/mins (rpm).
Embodiment 6: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.50 Pounds Per Hour, and the feeding rate of initiator is 0.025 Pounds Per Hour, and screw speed is 150 rev/mins.
Embodiment 7: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.75 Pounds Per Hour, and the feeding rate of initiator is 0.030 Pounds Per Hour, and screw speed is 150 rev/mins.
Embodiment 8: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 1.0 Pounds Per Hours, and the feeding rate of initiator is 0.038 Pounds Per Hour, and screw speed is 150 rev/mins.
Embodiment 9: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.50 Pounds Per Hour, and the feeding rate of initiator is 0.025 Pounds Per Hour, and screw speed is 50 rev/mins.
Embodiment 10: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.50 Pounds Per Hour, and the feeding rate of initiator is 0.025 Pounds Per Hour, and screw speed is 100 rev/mins.
Embodiment 11: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.50 Pounds Per Hour, and the feeding rate of initiator is 0.025 Pounds Per Hour, and screw speed is 200 rev/mins.
Embodiment 12: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.50 Pounds Per Hour, and the feeding rate of initiator is 0.025 Pounds Per Hour, and screw speed is 150 rev/mins.
Embodiment 13: the feeding rate of methacrylic acid 2-hydroxyl ethyl ester is 0.50 Pounds Per Hour, and the feeding rate of initiator is 0.025 Pounds Per Hour, and screw speed is 150 rev/mins.
According to the step of embodiment 1-4, with every kind of reaction product purifying and be pressed into film and be grafted to the weight percent of the methacrylic acid 2-hydroxyl ethyl ester on the LLDPE with mensuration with the FT-IR analytical test.Use is used for the linear regression calibration curve of linear low density polyethylene and measures the amount that is grafted to the methacrylic acid 2-hydroxyl ethyl ester on the linear low density polyethylene.Its grafting level and grafting efficiency the results are shown in the following table 2.
Table 2
| Embodiment | District's temperature, ℃ | FT-IR ratio | Percentage of grafting % | Grafting efficiency % |
| ?5 | ?180，200，200，200 | ?0.0723 | ?2.4 | ?49 |
| ?6 | ?180，200，200，200 | ?0.208 | ?7.7 | ?77 |
| ?7 | ?180，200，200，200 | ?0.387 | ?14.6 | ?97 |
| ?8 | ?180，200，200，200 | ?0.527 | ?20 | ?100 |
| ?9 | ?180，200，200，200 | ?0.0171 | ?0.3 | ?3 |
| ?10 | ?180，200，200，200 | ?0.151 | ?5.5 | ?55 |
| ?11 | ?180，200，200，200 | ?0.228 | ?8.4 | ?84 |
| ?12 | ?170，180，180，180 | ?0.273 | ?10 | ?100 |
| ?13 | ?180，210，210，210 | ?0.231 | ?8.5 | ?85 |
The comparative example A
(can be with a kind of polyethylene polymer available from Montell with melt flow index of 35dg/min, Three Little Falls Center, 2801 Centerville Rd., Wilmington Delaware) sends in the Haake twin-screw extruder with 5.0 Pounds Per Hours feeding rate.Use gel permeation chromatography (GPC) analysis, record the number-average molecular weight (M that described polypropylene has 60100g/mol
n), the weight-average molecular weight (M of 166800g/mol
w) and 2.78 polymolecularity (M
w/ M
n).Screw speed is located at 150rpm, and the temperature in four districts is located at 170,180,180,180 ℃ respectively.
Comparative Examples B
With 0.026 Pounds Per Hour peroxide initiator feeding rate, according to comparative example A's step extruded polypropylene.By gpc analysis, record M
nBe 40900g/mol, M
wBe 90700g/mol, polymolecularity is 2.22.These numerical value show that adding radical initiator has caused polyacrylic severely degrade.
Embodiment 14-20
Use (described in the embodiment 5-13) Haake extrusion machine extruding comparative example A's polypropylene.Screw speed is located at 150rpm, and the temperature in four districts is located at 170 ℃, 180 ℃, 180 ℃ and 180 ℃.The feeding rate of acrylic resin, methacrylic acid 2-hydroxyl ethyl ester and initiator (Pounds Per Hour) list in the following table 3.
Table 3
| Embodiment | Acrylic resin | ?HEMA | Initiator |
| ?14 | ?4.7 | ?0.49 | ?0.014 |
| ?15 | ?4.8 | ?0.49 | ?0.025 |
| ?16 | ?4.8 | ?0.49 | ?0.048 |
| ?17 | ?5.0 | ?0.52 | ?0.026 |
| ?18 | ?4.8 | ?0.96 | ?0.025 |
| ?19 | ?9.0 | ?0.96 | ?0.07 |
| ?20 | ?10.3 | ?0.96 | ?0.065 |
According to the step of embodiment 1-4, with the weight percentage of every kind of reaction product purifying and analytical element oxygen.Then will be in each sample the weight percentage of oxygen be determined at the weight percentage of grafted methacrylic acid 2-hydroxyl ethyl ester in each sample divided by the weight fraction (0.369) of oxygen in methacrylic acid 2-hydroxyl ethyl ester.Grafting level and grafting efficiency the results are shown in the following table 4.The elemental oxygen content of each sample is by Galbraith Laboratories, Inc.Knoxville, and Tennessee measures.
Table 4
| Embodiment | Weight % percentage of grafting | Grafting efficiency |
| ?14 | ?1.9 | ?18 |
| ?15 | ?5.6 | ?55 |
| ?16 | ?5.9 | ?58 |
| *17 | ?6.2 | ?59 |
| ?18 | ?10.6 | ?53 |
| ?19 | ?4.3 | ?40 |
| ?20 | ?3.1 | ?33 |
*Measure the M that this modified polypropene has 55300g/mol by GPC
n, 146900g/mol M
wWith 2.66 polymolecularity.This shows that using the inventive method that methacrylic acid 2-hydroxyl ethyl ester is grafted on the polypropylene can't cause polyacrylic obvious degradation.
Embodiment 21
Use is similar to 30 millimeters twin-screw extruder (Werner ﹠amp of the tool vacuum devolatilization of the above-mentioned embodiment of being used for 1-4; Pfleiderer, ZSK-30) extruding comparative example A's polypropylene, but these points exception is arranged.Described extrusion machine has total processing length of 1228 millimeters.Unreacted monomer removes by the end of vacuum devolatilization at extrusion machine.The acrylic resin feeding rate is that 25 Pounds Per Hours, methacrylic acid 2-hydroxyl ethyl ester monomer feed speed are that 2.25 Pounds Per Hours, initiator feed rate are 0.125 Pounds Per Hour.Screw speed is 300rpm, and all barrel zone temperatures are located at 190 ℃.The component charging that adds extrusion machine comprises methacrylic acid 2-hydroxyl ethyl ester monomer is injected into the injection port that is arranged in melt polypropylene.Initiator is injected in a back injection port in the fusing blend.The polymkeric substance wire rod that obtains cools off in water-bath, granulates and removed moisture in dry 18 hours under 29 inches Hg vacuum.The weight percentage of the grafting methacrylic acid 2-hydroxyl ethyl ester that records by elemental oxygen content is 2.57.
Although oneself is illustrated the present invention with reference to embodiment preferred, those skilled in the art will appreciate that and to carry out under the situation that does not deviate from spirit of the present invention variously substituting, deletion, change and modification.Therefore, should think that previous embodiment just is used to illustrate the present invention, rather than limitation of the invention.
Claims (6)
1. modified polyolefin compositions comprises polyolefin homopolymer and remaining grafted methacrylic acid 2-hydroxyl ethyl ester of about 70-95% (weight).
2. the composition of claim 1, wherein said grafted polyolefine is selected from: ultrahigh molecular weight polyethylene(UHMWPE), high density polyethylene(HDPE), ultra-low density polyethylene, new LDPE (film grade), linear low density polyethylene and polypropylene.
3. the composition of claim 2, wherein said graft polyolefin have under 2.16kg and 190 ℃ greater than about 0.01 minute Grams Per Minute (dg/min) to the melt index of about 100 minutes Grams Per Minutes.
4. the composition of claim 2, wherein said polyolefine have 2.16kg and 190 ℃ down about 0.05-25 divide the melt indexs of Grams Per Minute.
5. the composition of claim 1, the amount that wherein is present in the methacrylic acid 2-hydroxyl ethyl ester in the described composition are that 10% (weight) is to about 25% (weight).
6. the composition of claim 1, the amount that wherein is present in the methacrylic acid 2-hydroxyl ethyl ester in the described composition are that 10% (weight) is to about 20% (weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180618 CN1240456A (en) | 1996-10-18 | 1997-09-30 | Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/733,551 | 1996-10-18 | ||
| CN 97180618 CN1240456A (en) | 1996-10-18 | 1997-09-30 | Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1240456A true CN1240456A (en) | 2000-01-05 |
Family
ID=5177765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97180618 Pending CN1240456A (en) | 1996-10-18 | 1997-09-30 | Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1240456A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393790C (en) * | 2004-02-03 | 2008-06-11 | 住友化学工业株式会社 | Method for preparing modified polyolefin resin |
| CN103160022A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Special polyolefin resin composition for pipes |
| CN103160006A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Polyethylene resin composition special for pipes |
-
1997
- 1997-09-30 CN CN 97180618 patent/CN1240456A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393790C (en) * | 2004-02-03 | 2008-06-11 | 住友化学工业株式会社 | Method for preparing modified polyolefin resin |
| CN103160022A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Special polyolefin resin composition for pipes |
| CN103160006A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Polyethylene resin composition special for pipes |
| CN103160022B (en) * | 2011-12-15 | 2015-02-25 | 中国石油天然气股份有限公司 | Special polyolefin resin composition for pipes |
| CN103160006B (en) * | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Polyethylene resin composition special for pipes |
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