CN1033961C - Method for molding syndiotactic polypropylene and molded article - Google Patents
Method for molding syndiotactic polypropylene and molded article Download PDFInfo
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Abstract
A method for molding a polypropylene or a propylene copolymer having a syndiotactic structure which comprises the steps of melting, molding, if desired, quenching and then stretching a propylene homopolymer or a copolymer of propylene and a small amount of ethylene or another alpha -olefin which has a substantially syndiotactic structure, or a mixture of the same and a small amount of a polypropylene having a substantially isotactic structure. The molded and stretched article can be heated at a temperature of a molding temperature or more, while a load is applied to the article. Furthermore, the molded and stretched article, if desired, can be treated with a hydrocarbon vapor, while a load is applied to the article. The molded article obtained by the method of the present invention has a novel crystalline structure.
Description
The present invention relates to the preparation method and the mechanograph of syndiotactic polypropylene mechanograph.In more detail, the method of moulding of the syndiotactic polypropylene that the present invention relates to comprises the propylene that syndiotactic propylene homopolymers, tacticity that tacticity is higher are higher and the syndiotaxy copolymer of small amount of ethylene or another kind of alpha-olefin, the perhaps mixture of they and isotactic polypropylene, carry out fusion, the molded and step that stretches, the invention still further relates to the mechanograph that makes thus.
Syndiotactic polypropylene has been known for a long time for people, yet the syndiotactic polypropylene syndiotacticity that low temperature polymerization makes in the presence of the typical catalyst that contains vfanadium compound, ether and organo-aluminum compound is poor, and has elastomer shape characteristic.Therefore, the polypropylene that makes does not so almost have the characteristic of syndiotactic polypropylene, recent years, people such as J.A.Ewen have found the good polypropylene of tacticity first, the ratio that is syndyotactic five one group is greater than 0.7 polypropylene, it can use the transistion metal compound that contains asymmetric dentate with the catalyst of Lv oxane makes (J.Am.Chem.Soc.Vol.110, P6255-6256,1988).
With the molded syndiotactic polypropylene that makes by said method of Universal Die method for making, basically have syndyotactic propylene and ethene or another kind of alpha-olefin copolymer or and they and a small amount of mixture of isotactic polypropylene basically, the impact resistance of prepared mechanograph is quite good, but rigidity is not enough, therefore, this mechanograph is ungood aspect the balance of physical property.
The purpose of this invention is to provide the method for the mixture of the copolymer of a kind of molded syndyotactic Noblen or propylene and small amount of ethylene or another kind of alpha-olefin or they and isotactic polypropylene, this method is easy to make the high and good mechanograph of physical property of degree of crystallinity.
Another object of the present invention provides a kind of mechanograph with novel crystal structure and good physical, and it can be made by aforesaid propylene homopolymers or copolymer or mixture.
According to the present invention, provide following method of moulding and mechanograph.
The method of molded syndiotactic polypropylene comprises syndyotactic Noblen basically, the copolymer of syndyotactic propylene and small amount of ethylene or another kind of alpha-olefin or they and to be essentially the polyacrylic mixture fusion of isotactic structure, step molded and that stretch on a small quantity poly-basically.
The polypropylene mechanograph that is essentially trans zigzag crystal structure is that lattice paprmeter is the rhombic system of a=5.22, b=11.17 and c=5.06 , and it can be by fusion, molded, the stretch copolymer be essentially syndyotactic Noblen, syndyotactic propylene and small amount of ethylene or another kind of alpha-olefin or they and be essentially isotactic polypropylene miser on a small quantity and make then.
Record lattice paprmeter a=5.72 with X-ray diffraction method, b=7.64 and c=11.6 , α=73.1 °, the anorthic system polypropylene mechanograph of β=88.8 ° and γ=112.0 °, be by fusion and molded be syndyotactic polypropylene, above-mentioned copolymer or they basically and be essentially isotactic polyacrylic mixture on a small quantity make, if desired, the material of the quenching and the molded mistake that stretches is used the hydrocarbon compound steam treatment then.
Fig. 1 is the X-ray diffraction spectrum of embodiment 1 coupons that do not stretch.
Fig. 2 is the X-ray diffraction spectrum of comparative example 1 coupons that do not stretch.
Fig. 3 is the X-ray diffraction spectrum of embodiment 3 fibers that do not stretch.
Fig. 4 is the X-ray diffraction spectrum of comparative example 2 fibers that do not stretch.
Fig. 5 is with the embodiment 4 of the garden tubular camera fiber photo of drawing of fiber not.
Fig. 6 is the photo at 25 ℃ of fibers that stretched with the embodiment 4 of garden tubular camera.
Fig. 7 be with the embodiment 4 of garden tubular camera at 120 ℃ of fiber photos that stretched.
Fig. 8 is the photo with the fiber stretching of the embodiment 8 of garden tubular camera and that handled with benzene vapour.
Fig. 9 be from take the crystal structure of the fiber that records of fiber photo.
Among the present invention, have basically that the Noblen of syndiotactic structure is the crystalline polypropylene with high syndiotactic structure, wherein, in 1,2,4-trichloro-benzene solution, under 135 ℃, record13In the C-NMR absorption spectrum, at about 20.2ppm The first by five one group of structure generations of syndiotaxy that (take tetramethylsilane as the basis) observed The base peak intensity be all methyl total peak intensity 0.5 or bigger, be preferably 0.7 Or bigger, 10% of above-mentioned crystalline polypropylene (weight) or still less dissolve in first at room temperature In the benzene. Have the basically copolymer of syndyotactic propylene and ethene or another kind of alpha-olefin, Be contain the ethene except propylene of 20% (weight) or less amount or alpha-olefin, also Have a high syndyotactic copolymer, wherein measuring similarly13C-NMR In the absorption spectrum, the peak intensity of observing at about 20.2ppm is for all propylene units Total peak intensity that methyl produces 0.3 or bigger, be preferably 0.5 or bigger.
Above-mentioned polypropylene or propylene copolymer with syndiotactic structure, can contain asymmetric The transistion metal compound of dentate is with there is down polypropylene or third in the catalyst of Lv oxane Alkene and ethene or another kind of alpha-olefin and make.
Example with transistion metal compound of Asymmetry coordination base comprises that isopropyl (encircles penta 2 Thiazolinyl-1-fluorenyl) hafnium dichloride and isopropyl (cyclopentadienyl group-1-fluorenyl) dichloro Change zirconium, they have narration in the people's such as above-mentioned J.A.Ewen document. In addition, aluminium The example of oxane comprises with molecular formula R-(ALRO)nA-R
2OrThe compound of (R is the hydrocarbon residue of 1-3 carbon atom in the formula) expression. Being specially adapted to Lv oxane of the present invention is that R is that methyl Lv oxane and n are 5 or bigger, excellent Elect 10 or bigger De Lv oxane as. The consumption of Lv oxane is 10 of transistion metal compound-1,000,000 mole doubly, is generally 50-5, and 000 mole doubly.
The another kind of catalyst different from the structure of above-mentioned catalyst is used for the propylene homopolymerization as long as work as it The time, it is 0.7 or bigger polyacrylic that the ratio with five one group of syndiotaxy can be provided, Equally also can be used for the present invention.
Do not have particular restriction for polymerization technique, can use various polymerization techniques, as using inertia The solvent polymeric of solvent does not have the polymerisation in bulk of atent solvent to know gas-phase polymerization basically. Usually poly-Close temperature from-100-200 ℃, polymerization pressure be atmosphere be pressed onto 100 kilograms/ Centimetre2, preferred temperature is-100-100 ℃, and pressure is that atmosphere is pressed onto 50 kilograms per centimeter2。
Can be used for comprising 4-20 with the example of other alpha-olefin of copolymerization of propylene reaction The alpha-olefin of carbon atom. The exemplary of these alpha-olefins is linear alpha-olefins, such as fourth Alkene-1, amylene-1, hexene-1, heptene-1, octene-1, nonylene-1, the last of the ten Heavenly stems Alkene-1, undecene-1, dodecylene-1, tridecylene-1, tetradecene-1,15 carbenes-1, hexadecene-1 and vaccenic acid-1 and side chain alpha-olefin, Such as 3-methyl butene-Isosorbide-5-Nitrae-methylpentene-1 and 4,4-dimethyl pentene-1.
Above-mentioned alpha-olefin unit is preferably 20% (weight) or littler with respect to the ratio of copolymer, and particularly preferred is 10% (weight) or littler.When the ratio of other alkene surpasses 20% (weight), the rigidity variation of mechanograph.Condition to copolymerization does not have particular restriction, can use and the identical polymeric reaction condition of the equal polymerization of propylene.
In order further to improve the syndiotacticity of gained (being total to) polymer, the solvent wash of available energy dissolving or dispersion low molecular weight atactic component is somebody's turn to do (being total to) polymer, the example of these solvents comprises the varsol of 3-20 carbon atom, as propylene, aliphatic saturated hydrocarbon, aromatic hydrocarbons and halogenated hydrocarbons, the alcohols of 1-20 carbon atom, the ethers of 2-20 carbon atom and ester class.Washing methods is not particularly limited, and can wash at 0-100 ℃.
The homopolymerization of propylene amounts to poly-reaction and is undertaken by the one-step polymerization reaction usually.The molecular weight distribution that makes like this is narrow, is about 1.5～3.5 with gel permeation chromatography at the ratio (hereinafter referred is " MW/MN ") of weight average molecular weight with the number-average molecular weight of 135 ℃ of polymer that record.Yet, (for example use two kinds of transistion metal compounds, it is effective that zirconium and hafnium compound are used in combination) can prepare the molecular weight distribution polymer of wide (molecular weight distribution is about 3.5～15), perhaps (being total to) mixed with polymers of two or more different molecular weights is made the wide polymer of molecular weight distribution, thereby, can use (being total to) polymer of MW/MN1.5 of the present invention～15.
The molecular weight of the polymer that the present invention uses is represented with inherent viscosity usually, at the preferably about 0.1-20 of 135 ℃ of inherent viscosities that record in 1,2,3,4-tetrahydro-naphthalene (hereinafter referred is " η "), particularly preferably is 0.5-10.0.
Among the present invention, the part of syndiotactic polypropylene or syndiotactic propylene copolymer (for example less than 50%, preferably 40% or still less) available isotactic polypropylene replaces, and in this case, can obtain the high mechanograph of rigidity.Under this situation, can use commercially available various isotactic polypropylene products.For the polypropylene of so-called high upright structure rule positivity is provided, can use following a kind of Preparation of Catalyst isotactic polypropylene, this catalyst contains titanium trichloride and organo-aluminum compound, perhaps is carried on titanium trichloride or titanium tetrachloride and organo-aluminum compound on the magnesium halide.The ratio that this polyacrylic isotaxy is five one group is preferably 0.9 or bigger.And, in the preferred isotactic polypropylene that uses, be preferably about 0.1-10 at 135 ℃ of η that in 1,2,3,4-tetrahydro-naphthalene solution, record, particularly preferably be about 0.5-5.In the method for the present invention, if the polyacrylic amount of isotactic structure is 50% (weight) or higher, then impact resistance is poor.
In the method for the present invention, be essentially the Noblen of syndiotactic structure and the copolymer of small amount of ethylene or another kind of alpha-olefin, or they and be essentially isotactic polyacrylic mixture on a small quantity, at first carry out heating and melting, be molded as given shape then.Method of moulding is not particularly limited, can uses crowded modulus method, compression moulding or injection molding.Consider this fact that stretches after molded, squeeze mould or blowing mould (wherein after extruding, can successfully stretch) and can preferentially select for use.
About syndiotactic polypropylene mechanograph before stretching, its crystal structure is important, not observing at about 7.1 places with X-ray diffraction method has the mechanograph of any diffracted ray to suit, even this is because do not determine it is under the situation of complete broached-tooth design in the goods after stretching, this mechanograph is easy to be stretched, and can obtain smooth surface and the good stretched goods of physical property after stretching.Observe at 7.1 places under the situation of mechanograph of strong diffracted ray, it is very difficult carrying out stretched operation." not observing diffracted ray " at this is not see diffracted ray fully, but say when with Cu-K alpha ray (it is the X-ray) from 5 ° to 50 ° when 2 θ scopes are measured, the intensity of diffracted ray, for example only be observed diffracted image maximum peak intensity 1/5 or littler.
By being easy to obtain this stretchable mechanograph through goods quenching fusion and mold pressing.The quenching degree depends on the tacticity of syndiotactic polypropylene, the composition of copolymer and molecular weight, typical cooldown rate is when the temperature of use (being total to) polymer is raised to 250 ℃, carry out cooling down operation with various cooldown rates, press differential scanning calorimeter then and heat up with 10 ℃/minute speed, the number of fusion endothermic peak is actually one.Usually cooldown rate is 50 ℃/minute or bigger.
Next step is with stretching at the mechanograph that 7.1 places do not observe any diffracted ray with X-ray diffraction method of making like this.The stretched operation temperature is not had specific (special) requirements, and stretched operation can carry out at normal temperatures, uses low rate of extension can obtain high draw ratio.Yet, much less,, can under heating condition, stretch in order to reduce tensile stress.Heating-up temperature should keep a period of time, makes to be stretching under such condition to carry out, so that do not occur strong diffracted ray with the measurement of X-ray diffraction method at about 7.1A place.The stretched operation temperature cans be compared to low 10 ℃ of polyacrylic fusing point most, particularly preferably is low 20 ℃.
Heating and fusion are after the mechanograph of quenching can stretch under the quite low temperature near room temperature, and particularly Yi Gao Yang stretches when stretching at low temperatures, and can obtain all is the polypropylene mechanograph of trans sawtooth crystal structure basically.And, under the situation of the syndiotactic polypropylene of molecular weight quite high (for example η is 1.0 or bigger), with quite high draw ratio.For example 3 times or bigger, being preferably 10 times or bigger draw ratio stretches and replaces with 100 ℃/minute or higher speed quenching, so that make obtained measure mechanograph that can't see any diffracted ray at about 7.1 places with the X-ray diffraction method, can all obtain the polypropylene of trans broached-tooth design basically.In order to be the goods of trans broached-tooth design basically, must stretch at low temperatures.If draft temperature surpasses 100 ℃, crystal structure changes, and can not all is the mechanograph that is trans broached-tooth design basically.About polyacrylic crystal structure, isotactic polypropylene is got helical structure, and the trans broached-tooth design of syndiotactic polypropylene (G.Natta etc., Makromol.Chem.75 volume, 215 pages (1964)).Yet common syndiotactic polymerization alkene dissolves in hydro carbons in room temperature, for this reason, almost can not manage to use this syndiotactic polypropylene to do the crystalline polypropylene mechanograph.In addition, from the crystallography viewpoint, this syndiotactic polypropylene is not determined complete trans broached-tooth design as yet.On the contrary, can determine further that mechanograph of the present invention is the leveling saw toothing, when with the X-radiological survey X, its spectrum so strongly consequently be can't see another kind of crystal structure.
The mechanograph that has carried out stretch processing is crystal structure, is that lattice paprmeter is a=5.22, the rhombic system of b=11.17 and c=5.06 .
Among the present invention, the goods that drawn is crossed can be heat-treated to improve its degree of crystallinity and physical property.In order to improve degree of crystallinity and to improve the physical property that comprises rigidity, after the mold pressing, crystalline polymer is usually heat-treated by heating.In order to improve by heating only is that high syndyotactic polyacrylic degree of crystallinity must be heated to polypropylene the temperature near its fusing point, and needs the very long cycle, and the degree of crystallinity of gained is still not high enough as a result.On the contrary, stretch earlier before it is found that heating, can improve degree of crystallinity very effectively, although its reason is not clear.
The heat treatment temperature that the present invention uses is 50 ℃ or higher, is preferably 80 ℃ or higher, less than the fusing point of mechanograph, and greater than draft temperature.The preferable range of required heat time heating time depends on draft temperature.The preferable range of required heat time heating time depends on the fusing point of polymer, and heating-up temperature and draft temperature have no particular limits this, but in several seconds to tens hour scopes.Temperature is high more, and heat time heating time is short more, when heating-up temperature is 100 ℃ or when higher, heat time heating time several seconds in the dozens of minutes scope.
For degree of drawing mechanograph high and that in above-mentioned X-ray diffraction spectrum, obviously reduce at 7.1A place diffracted ray, perhaps by the goods of quenching after the heating/fusion (can't see diffracted ray at about 7.1 places or diffracted ray is very weak) are carried out the resulting mechanograph of cold stretch, when heating for about 100 ℃, heat time heating time is from a few minutes to the dozens of minutes.Therefore if heat after stretching, even very shortly also can obtain enough degree of crystallinity heat time heating time, and physical property also improves.Preferably the goods that stretched are fixed and under loaded situation, heat-treated, in case the mechanograph distortion.
In the present invention, the goods of available hydrocarbon compound steam treatment drawn.Even to the goods of shaggy stretching and the elongated article that obtains by those goods that were not stretched that stretch, all be effectively with steam treatment, so that reduce the great diffracted ray in 7.1 places on the X-ray diffraction spectrum.Be preferably in when goods remain under extended state and the loading condition with steam treatment and carry out, can prevent the mechanograph distortion like this, improve the transparency of the polymer of destroyed when stretching simultaneously.
The example that is used for the hydrocarbon compound of steam treatment comprises the saturated hydrocarbons and the unsaturated hydrocarbons of about 5-20 carbon atom, the halogenated hydrocarbon that part or all of hydrogen atom is replaced by halogen.Preferred hydrocarbon compound comprises saturated hydrocarbon compound, as pentane, and hexane, heptane, octane, nonane, decane and cyclohexane; Aromatic compound is as benzene,toluene,xylene, ethylbenzene, isopropylbenzene and cymene; With part hydrogen atom substituted halogen atom substituted compound.
This steam treatment can at room temperature be finished, but in order to shorten the processing time, heating also is an acceptable.Heating-up temperature is generally 100 ℃ or lower.This mainly is in order to prevent the mechanograph distortion.And the processing time is depended on treatment temperature, but in about 1 second to 100 hour scope, is preferably about 1 minute to 10 hours.
After the steam treatment, blow, if desired, under reduced pressure handle or heat treatment, can remove the hydrocarbon compound that is included in the mechanograph with nitrogen or air.Wherein, make the mechanograph that carries out steam treatment, preferably under mechanograph applies the situation of load, heat-treat simultaneously, thereby improve the physical property of mechanograph in the temperature that is not higher than the m-isotactic polypropylene fusing point.
Have the substantial horizontal broached-tooth design if give the goods of stretching with the hydrocarbon compound steam treatment, then can obtain the polypropylene mechanograph of anorthic system state, lattice paprmeter is a=5.72, b=7.64, c=11.6 , α=73.1 °, β=88.8 ° and γ=112.0 °.So far and do not know such crystalline form, but its characteristic can be expected.In order to obtain above-mentioned crystalline form, the derivative that the aromatic compound of 6-25 carbon atom can be preferably used as the benzene that hydrocarbon compound, particularly benzene or its part or all of hydrogen atom replaced by alkyl is preferably used.At 50 ℃ or low temperature more, with hydrocarbon compound steam treatment a few minutes to tens day, preferably about 1 hour to 10 days.
In method of moulding of the present invention, the commonly used additive of molded polyolefin can with (being total to) mixed with polymers, the example of additive comprises antioxidant, UV absorbers and crystallization nucleating agent.All can be used for the present invention as long as can improve any nucleator of the crystallization temperature of syndiotactic polypropylene.Usually, spendable nucleator, its fusing point is higher than the fusing point of syndiotactic polypropylene, and with contacting of syndiotactic polypropylene can be low.Also can use the nucleator that is used for isotactic polypropylene.The example of nucleator comprises benzoic salt, the salt of benzylidene D-sorbite, phosphate, and quinacridone and high melting-point polyolefins, as polyvinyl cyclohexene, poly-(3-methyl butene), crystal polystyrene and poly-trimethyl-ethylene base silane.In addition, as talcum, inorganic compounds such as kaolin and mica also can be used as nucleator.The consumption of nucleator depends on the kind of crystallization nucleating agent, but is generally about 0.01ppm to 1% (weight) of polymer weight.
Method of moulding of the present invention can be used to make sheet, film, fiber, bottle, pipe or the like.
Below, reference example and comparative example illustrate in greater detail the present invention, but these embodiment do not should be understood to limitation of the present invention.
Embodiment 1
In 200 liters of autoclaves, add 80 liters of toluene, add 0.2 gram isopropyl (cyclopentadienyl group-1-fluorenyl) zirconium dichloride and 30 gram methyl aluminium oxanes (degree of polymerization 16.1, Toso AKZ0 Co., Ltd makes) again.This isopropyl (cyclopentadienyl group-1-fluorenyl) zirconium dichloride is prepared as follows: will change into lithium salts with the synthetic isopropyl cyclopentadienyl group-1-fluorenes of conventional method, and then itself and zirconium chloride be reacted, gained product again is recrystallized.Afterwards, propylene was at 3kg/cm
2Under-G the polyalcohol pressure 20 ℃ of polymerizations 2 hours.In resulting polymers, add methyl alcohol and methyl acetoacetate, handle this polymer at 30 ℃.Use the aqueous hydrochloric acid solution washing copolymer, filter then, obtain 5.6 kilograms of syndiotactic polypropylenes.According to
13C-NMR, the ratio that this polyacrylic syndiotaxy is five group is 0.935, and recording inherent viscosity in 135 ℃ of 1,2,3,4-tetrahydro-naphthalene solution is 1.45, and 1,2, recording MW/MN in the 4-trichloro-benzene is 2.2.
With 3.5-di-t-butyl-4-hydroxy-methylbenzene, calcium stearate and octadecyl-3-(3.5-di-tert-butyl-hydroxy phenyl) propionic ester joins in the polypropylene, its addition is respectively 0.1% (weight), 0.08% (weight) and 0.045% (weight), and make particle with extruder.Second step, at 200 ℃ with particle fusion and be pressed into the sheet of 1 millimeters thick, quenching in the water that sheet input that then will be such is 0 ℃.In quench step, recording the temperature fall off rate with the temperature sensor that inserts the sheet center is 250 ℃/minute.The X-ray diffraction spectrum of this sheet is shown in Fig. 1, locates to observe any diffracted ray at 7.1A (2 θ=12.5 °).Measure the physical property of this sheet then.Flexural rigidity: Kg/cm
2ASTMD-747 (23 ℃) tensile strength: kg/cm
2ASTMD-638 (23 ℃) elongation at break: % ASTMD-638 (23 ℃) cantilever-type impact strengths (otch): kgcm/cm ASTMD-638 (23 ℃-10 ℃) haze: % ASTMD-1003
Flexural rigidity is 5300kg/cm
2, tensile strength is 215kg/cm
2Elongation at break is 480%, and cantilever-type impact strength (23 ℃ ,-10 ℃) is respectively 14.0 and 3.8, and haze is 15%.
This sheet stretches 5 times at 10 ℃, and the physical property of measuring the stretching caudacoria is as follows:
Haze: % ASTMD1003
Tensile strength: kg/cm
2
Film after stretching is cut into the test film of 50mm * 20mm, draws this test film with 200 millimeters/minute tension force speed with tensile strength meter, and the mensuration tensile strength at break.
Percentage elongation: %
When measuring tensile strength, the percentage elongation of test piece when measuring fracture.
Tensile strength is 702kg/cm
2, percentage elongation is 113%, haze is 8.3%.
Test piece after will stretching in addition kept extended state 10 hours at 130 ℃, measured physical property then.As a result, tensile strength is 980kg/cm
2, percentage elongation is 45%, haze is 25%.
Embodiment 2
Except 80 ℃ stretch, all the other are undertaken by embodiment 1 identical method, and the result is that tensile strength is 680kg/cm
2, percentage elongation is 75%, haze is 22.5%.And then the goods after will stretching kept 10 hours at extended state at 130 ℃, measured its physical property then, and the result is that tensile strength is 950kg/cm
2, percentage elongation is 45%, haze is 42%.
Comparative example 1
Except using the sheet that the mechanograph cooling was made in 30 minutes, all the other are undertaken by embodiment 1 identical method.The X-ray diffraction spectrum of this sheet is shown in Fig. 2.At 10 ℃ this more than sheet stretching twice, is cut this sheet, can not continue again to stretch.Even 2.5 times of 80 ℃ of these sheets of stretching, cut this sheet then, can not stretch.
Embodiment 3
With calcium stearate and 2, in the syndiotactic polypropylene that 6-DI-tert-butylphenol compounds adding embodiment 1 makes, its ratio is calcium stearate and 2, the 6-DI-tert-butylphenol compounds is 10 parts, polypropylene is 10,000 parts and presses 10 parts of talcums again to 10,000 parts of polyacrylic ratios, add talcum, this mixture is made particle.Then, be that 40 millimeters, screw rod speed are 14 holes on 64 rev/mins the die orifice of extruder by garden tube diameter, carry out spinning at 220 ℃.To introduce quenching-10 ℃ of salt solution from the fibre bundle that die orifice comes out.The fibre number that obtains like this is a 370D/14 root fiber, and according to tension test, maximum intensity is 480 grams, and percentage elongation is 680%.The X-ray diffraction light of this fiber that use Cu-K alpha ray is measured is penetrated and is seen Fig. 3.
When fiber stretches 10 times the time at 25 ℃, maximum intensity is 780 grams, and percentage elongation is 25%.Further, when stretching for 120 ℃, maximum intensity is 680 grams, and percentage elongation is 20%.Comparative example 2
Except the fibre bundle from die orifice cools off in air, keep outside 5 hours at 120 ℃ then, all the other are undertaken by embodiment 3 identical methods.The X-ray diffraction spectrum of this fiber is seen Fig. 4.25 ℃ of stretching twices, fiber is cut off, even stretch 3 times at 120 ℃, fiber also is cut off.
Embodiment 4
Press calcium stearate and 2, each 10 parts of ratio of 6-DI-tert-butylphenol compounds to 10,000 parts of polypropylene, with calcium stearate and 2, in the polypropylene that 6-DI-tert-butylphenol compounds adding embodiment 1 makes, and press 10 parts of talcums to 10,000 part of polyacrylic ratio adds talcum, and this mixture is made particle.Then, be that 40 millimeters, screw rod speed are 14 holes on 64 rev/mins the extruder die orifice by garden tube diameter, carry out spinning at 220 ℃.To import quenching in-10 ℃ of salt solution from the fibre bundle of die orifice.The fibre number that obtains like this is a 370D/14 root fiber, and according to tension test, maximum intensity is 480 grams, and percentage elongation is 680%.
This fiber stretches 10 times the time at 25 ℃, and maximum intensity is 780 grams, and percentage elongation is 25%, and excellent transparency.On the contrary, 120 ℃ of these fibers that stretch (when stretching 6 times the time, therefore fibre cutting stretches 5 times), maximum intensity is 680 grams, and percentage elongation is 20%.The photo of drawing of fiber is not seen Fig. 5, sees Fig. 6 and Fig. 7 respectively at the photo of the fiber of 25 ℃ and 120 ℃ stretchings.
From these fiber photos as seen, the fiber of La Shening almost is not unbodied, be trans broached-tooth design at 25 ℃ of fibers that stretched, and for the fiber that stretched at 120 ℃, observed diffracted image is not trans broached-tooth design.
Embodiment 5
With 3.5-di-t-butyl-4-hydroxy-methylbenzene, calcium stearate and octadecyl-3-(3.5-di-tert-butyl-hydroxy phenyl) propionic ester joins in the polypropylene that embodiment 1 makes, it is not 0.1% (weight) that addition is divided in addition, 0.08% (weight) and 0.045% (weight) are with this mixture pelleting.Then, 200 ℃ of fusions and to be pressed into thickness be 1 millimeter sheet.Measure the physical property of this sheet with the method identical with embodiment 1, result, flexural rigidity are 5300kg/cm
2, tensile strength is 240kg/cm
2, elongation at break is 520%, and cantilever-type impact strength (23 ℃ ,-10 ℃) is respectively 14.2 and 3.6, and haze is 28%.
This sheet stretches 3 times at 30 ℃, measures the physical property of gained oriented film.As a result, tensile strength is 650kg/cm
2, percentage elongation is 78%, haze is 32%.The film of this stretching is placed an airtight container at extended state, handled 6 hours with toluene vapor at 30 ℃.This film is measured its physical property 80 ℃ of Bao Chi Yang extended states 5 hours.As a result, tensile strength is 690kg/cm
2, percentage elongation is 60%, haze is 12%.As can be known from these results, handle the transparency of having improved film with toluene vapor.
On the other hand, when this film carried out heat treated and handles without toluene vapor at extended state, tensile strength was 680kg/cm
2, percentage elongation is 55%, and haze is 35%, and transparency is not improved.
Embodiment 6
Except at 120 ℃ of drawing sheets, to handle outside 30 minutes with toluene vapor at 50 ℃ then, all the other are undertaken by embodiment 5 identical methods, and in the case, tensile strength is 680kg/cm
2, percentage elongation is 85%, haze is 18%, is 38% with the haze before the O for toluene.
Embodiment 7
Except replacing the toluene with dimethylbenzene, all the other are undertaken by embodiment 5 identical methods, and under this situation, tensile strength is 685Kg/cm
2, percentage elongation is 70%, haze is 14%.
Embodiment 8
Press calcium stearate and 2, the 6-DI-tert-butylphenol compounds each 10 parts to polypropylene.10,000 parts ratio with calcium stearate and 2, in the polypropylene that 6-DI-tert-butylphenol compounds adding embodiment 1 makes, to 10,000 parts of polyacrylic ratios, adds talcum, with this mixture pelleting by 10 parts of talcums again.Then, be that 40 millimeters, screw rod speed are that spinning is carried out at 220 ℃ in 14 holes on 64 rev/mins the extruder die orifice by garden tube diameter.To import in-10 ℃ of salt solution from the fibre bundle of mould and carry out quenching.The fibre number that makes like this is a 370D/14 root fiber, and according to tension test, maximum intensity is 480 grams, and percentage elongation is 680%.
This fiber stretches 10 times the time at 25 ℃, and maximum intensity is 780 grams, and percentage elongation is 25%, and the transparency of fiber is good especially.Fiber after stretching was handled 24 hours in 40 ℃ of benzene vapours, and maximum intensity is 820 grams, and percentage elongation is 20%.See Fig. 8 with the fiber photo that garden tubular camera is taken.See Fig. 9 from the crystal structure that fiber photo measurement result is determined.
Embodiment 9
In 2 liters of autoclaves, with 10 milligrams of isopropyls (cyclopentadienyl group-1-fluorenyl) zirconium dichloride of not purifying with to react the degree of polymerization that obtains by six hydrated copper sulfates and trimethyl aluminium in toluene be that 15 methyl Lv oxane 1.34 restrains and is dissolved in 1 liter of toluene, propylene is at 2Kg/cm
2Under-G the polymerization pressure 50 ℃ of polymerizations 1 hour.After polymerisation is finished, clean out unreacted propylene, collect the gained slurries, 30 ℃ of filtrations, with 500 milliliters of toluene wash 5 times, drying under reduced pressure obtains 98 and restrains polypropylene then.According to
13C-NMR, the ratio that this polypropylene syndiotaxy is five group is 0.902, and η is 0.88, and MW/MN is 2.2.
This polypropylene was cooled to 20 ℃ at 250 ℃ of sheets that are molded into 1 millimeters thick with the sheet of making in 5 minutes, then 100 ℃ of stretching twices.According to X-ray diffraction spectrum, by current stretching, the intensity of viewed diffracted ray at about 7.1 places is reduced to about 1/2.Measure the physical property of this sheet.The result is that the tensile strength of the sheet that do not stretch is 580Kg/cm
2, percentage elongation is 420%, and haze is 15.2%, and the sheet tensile strength after the stretching is 660Kg/cm
2, percentage elongation is 85%, haze is 22.6%.
In addition, the sheet of stretching kept extended state 30 minutes at 130 ℃, measured its physical property, and the result is that tensile strength is 780Kg/cm
2, percentage elongation is 55%, and haze is 26%, and the degree of crystallinity that records from X-ray diffraction spectrum is 78%.Otherwise the degree of crystallinity of the sheet of La Shening not is 52%, because the diffracted ray of seeing is very wide, the degree of crystallinity of stretching rear panel is unclear, but is about 40%.Therefore, by heat treatment degree of crystallinity be improved significantly, physical property has also obviously strengthened.
Embodiment 10
Except 110 ℃ of heat treatments 1 hour, all the other are undertaken by embodiment 9 identical methods, obtain a film subsequently.About the physical property of this film, tensile strength is 760kg/cm
2, percentage elongation be 48% and haze be 28%.In addition, the degree of crystallinity that records from X-ray diffraction spectrum is 72%.
Embodiment 11
Press calcium stearate and 2, each 10 parts of ratio of 6-DI-tert-butylphenol compounds to 10,000 parts of polypropylene, with calcium stearate and 2, in the syndiotactic polypropylene that 6-DI-tert-butylphenol compounds adding embodiment 9 makes, and press 10 parts of talcums to 10,000 part of polyacrylic ratio adds talcum, with this mixture pelleting.Subsequently, by garden tube diameter is 40 millimeters, the screw rod speed is that 14 holes on 64 rev/mins the extruder die orifice are spun than silk, fibre bundle from die orifice cools off in air, the fibre number that obtains like this is a 370D/14 root fiber, according to tension test, maximum intensity is 480 grams, and percentage elongation is 150%.
This fiber is 60 ℃ of stretching twices, and according to tension test, maximum intensity 560 restrains, and percentage elongation is 40%.According to X-ray diffraction spectrum, by stretching, be reduced to about 1/2 in the intensity of the observed diffracted ray in about 7.1 places.In addition, this fiber remained on extended state 2 hours at 100 ℃, and according to tension test, maximum intensity is 620 grams, and percentage elongation is 15%, and degree of crystallinity is 72%.
Embodiment 12
In 2 liters of autoclaves, 2.5 milligrams of isopropyls (cyclopentadienyl group-1-fluorenyl) zirconium dichloride and 0.34 gram aluminium methyl oxane (degree of polymerization is 16.1, is produced by TOSO AKZO Co., Ltd) are dissolved in 1 liter of toluene.This isopropyl (cyclopentadienyl group-1-fluorenyl) zirconium dichloride is prepared as follows: isopropyl cyclopentadienyl group-1-fluorenes that conventional method is synthetic is transformed into lithium salts, and itself and zirconium chloride are reacted, and the product of gained is recrystallized then.Subsequently, in this solution, add propylene, reach 3Kg/cm until pressure at 20 ℃
2-G, per 10 minutes, the speed adding ethene with 1.0 Grams Per Minutes added for 10 seconds at every turn.In addition, add propylene again in solution, making polymerization pressure is 3Kg/cm
2-G, copolyreaction was carried out 3.5 hours.Then, in solution, add methyl alcohol and acetoacetic ester, handle,, filter then, obtain containing the propylene-ethylene copolymer of 2.0% (weight) ethylene unit with the aqueous hydrochloric acid solution washing at 30 ℃.
This copolymer
13In the C-NMR absorption spectrum, be 0.89 of total peak intensity of being produced by the methyl of all propylene units at the observed peak intensity of 20.2ppm, η is 1.24, and 1,2, the MW/MN that records in the 4-trichloro-benzene solution is 2.3.
Press the identical method of embodiment 1, this copolymer mold pressing is in blocks, and measure the physical property of this sheet, result, flexural rigidity are 4300kg/cm
2, tensile strength is 198kg/cm
2, elongation at break is 635%, and cantilever-type impact strength (23 ℃ ,-10 ℃) is respectively 18.0 and 4.2, and haze is 12%.
This sheet stretches under the identical condition of embodiment 1, measures the physical property of the sheet after stretching, and the result is that tensile strength is 580kg/cm
2, percentage elongation is 150%, haze is 6.2%.
Embodiment 13
10, in the syndiotactic polypropylene that 000 part of (weight) embodiment 1 makes, add 10 parts (weight) commercially available isotactic polypropylene particle (trade (brand) name JS-1429, make by Mitsui Toatsu chemical company), 10 parts of (weight) 3.5-di-t-butyl-4-hydroxy-methylbenzenes, 8 parts of (weight) calcium stearates and 4.5 parts of (weight) octadecyl-3-(3.5-di-tert-butyl-hydroxy phenyl) propionic ester are with this mixture pelleting.Subsequently, 200 ℃ with particle fusion, extruding, and the sheet that obtains dropped in 0 ℃ of water.
This sheet stretches 5 times at 10 ℃, measures its physical property, and the result is that tensile strength is 910kg/cm
2, percentage elongation be 58% and haze be 12.5%.
Claims (7)
1. one kind prepares the polypropylene that has syndiotactic structure basically or the method for propylene copolymer mechanograph, and this method comprises:
With acrylic polymers fusion and the molded mechanograph that becomes,
Described mechanograph is carried out quenching with 50 ℃/second or bigger cooling velocity,
Then, the goods of described quenching are stretched,
Described acrylic polymers is selected from: the Noblen that has syndiotactic structure basically, propylene and ethene or contain the copolymer of other alpha-olefin of 4-20 carbon atom, and described homopolymers or described copolymer with have the polyacrylic mixture of isotactic structure basically in a small amount.
Described Noblen is 1,2, in the C-NMR absorption spectrum of this homopolymers of measuring in the 4-trichloro-benzene solution, the peak intensity of the observed methyl by the syndiotactic structure generation of about 20.2ppm (based on tetramethylsilane) be the total peak intensity of all methyl 0.7 or bigger
The copolymer of other alpha-olefin of a described propylene and ethene or 4-20 carbon atom, 1,2, in the c-NMR absorption spectrum of this copolymer of measuring in the 4-trichloro-benzene solution, the about observed peak intensity of 20.2ppm (based on tetramethylsilane) be total peak intensity that methyl was produced of all propylene units 0.5 or bigger.
2. method according to claim 1, wherein, ratio with the weight average molecular weight of the Noblen that is essentially syndiotactic structure of gel permeation chromatography or copolymer and number-average molecular weight is 1.5-15, at 135 ℃ 1,2,3, the homopolymers of measuring in the 4-tetrahydronaphthalene solution or the inherent viscosity of copolymer are 0.1-20.
3. method according to claim 1, wherein the mechanograph of first quenching before stretching in the X-ray spectrum, does not have diffracted ray at the 7.1A place.
4. method according to claim 1, wherein, described stretching be than the fusing point of Noblen or copolymer at least low 10 ℃ temperature carry out.
5. method according to claim 1, wherein, to have syndiotactic structure basically, at 135 ℃ 1,2,3, the inherent viscosity of measuring in the 4-tetrahydronaphthalene solution be 0.1 or bigger Noblen or copolymer carry out fusion, molding, under 100 ℃ or lower temperature, stretch 3 times or more times then, and do not carry out quenching.
6. method according to claim 1 wherein, is heat-treated the molded and goods that stretch being higher than draft temperature and being lower than under the temperature of mechanograph fusing point, applies a load to these goods simultaneously.
7. the polypropylene that has syndiotactic structure basically of making by any one described method among the claim 1-6 or the mechanograph of propylene copolymer, it is the crystal structure of the orthogonal thereto crystallographic system of trans broached-tooth design basically that described mechanograph has, according to X-ray diffraction, its lattice paprmeter is a=5.22, b=11.17, c=5.06A.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9230490A JP3036783B2 (en) | 1990-04-09 | 1990-04-09 | Polypropylene moldings |
| JP9230590A JP2818252B2 (en) | 1990-04-09 | 1990-04-09 | Syndiotactic polypropylene drawing method |
| JP92305/90 | 1990-04-09 | ||
| JP92304/90 | 1990-04-09 | ||
| JP192929/90 | 1990-07-23 | ||
| JP211584/90 | 1990-08-13 | ||
| JP306136/90 | 1990-11-14 | ||
| JP30613690A JP2818284B2 (en) | 1990-11-14 | 1990-11-14 | Molded product of polypropylene and method for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95121332A Division CN1059384C (en) | 1990-01-14 | 1995-12-15 | Method for molding syndiotactic polypropylene and molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1056274A CN1056274A (en) | 1991-11-20 |
| CN1033961C true CN1033961C (en) | 1997-02-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91102948 Expired - Fee Related CN1033961C (en) | 1990-04-09 | 1991-04-09 | Method for molding syndiotactic polypropylene and molded article |
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| Country | Link |
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| CN (1) | CN1033961C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468440B1 (en) * | 1994-05-06 | 1997-04-08 | Exxon Chemical Patents Inc | Process of making oriented film or structure |
| IL116430A (en) * | 1994-12-19 | 2000-08-13 | Hercules Inc | Process for preparing a polypropylene containing fiber |
| ATE192513T1 (en) * | 1996-02-12 | 2000-05-15 | Fina Research | POLYPROPYLENE FIBERS |
| US6074590A (en) * | 1997-07-28 | 2000-06-13 | Fina Technology, Inc. | Process of making a bicomponent fiber |
| US5948334A (en) * | 1997-07-31 | 1999-09-07 | Fiberco, Inc. | Compact long spin system |
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| CN1056274A (en) | 1991-11-20 |
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