CN1025625C - Crystalline p p sheet - Google Patents

Abstract

The present invention relates to crystal polypropylene which is characterized in that the crystal polypropylene comprises a vinyl naphthene polymer (by vinyl naphthene unit), wherein the vinyl naphthene polymer at least contains six carbon atoms, and the content of the vinyl naphthene polymer is from 0.05 ppm to 1% (by weight). Because of having favorable toughness and favorable transparency, the sheet material is suitable to be made into various products, such as various packing containers, disks, etc.

Description

Crystalline p p sheet

The present invention relates to the crystalline p p sheet of excellent in toughness and transparency.

Crystalline p p sheet is being used to every field more and more, and this is not only because its production cost is low, but also because it has favorable mechanical performance and good optical performance, secondly is because its plasticity-and moistureproofness.But these characteristics are not very good in some application facet.For example, crystalline p p sheet is compared with polychlorovinyl sheet material with polystyrene in some Application Areas, needs to improve its toughness and transparency.

For improving polyacrylic toughness and transparency trial had several times been arranged.At present, people know, reach above effect, can add the aluminium salt and the sodium salt (Japanese patent application (OPI) No.80329/83) that belong to aromatic carboxylic acid, or add other aromatic carboxylic acid, as the derivative (Japanese patent laid-open publication gazette No.12460/80 and Japanese patent application (OPI) No.129036/83) of aromatic phosphoric acid metal-salt and Sorbitol Powder.They are equivalent to form the reagent (hereinafter being referred to as nucleation reagent) of nucleus, are used for improving the toughness and the transparency of crystalline p p sheet.Special term OPI used herein refers to disclosed uncensored Japanese patent application.

In the above mentioned nucleation reagent, the nucleogenesis of sorbitol derivatives is best.But it also has disadvantageous one side, and that is separated out from polypropylene material after being exactly the derivative molding processing of Sorbitol Powder easily, and the polypropylene finished product of molding are bleached, and also can produce a kind of niff in the molding course of processing.Obviously, the range of application of sorbitol derivatives is limited.In addition, aromatic carboxylic acid aluminium salt is widely used as nucleation reagent.But this crystalline p p sheet that contains aluminium salt can reduce owing to moisture absorption causes its transparency after depositing one long period.

Japanese patent laid-open publication gazette No.32430/70 points out that propylene carries out the transparency that copolyreaction can improve crystalline p p sheet with random copolymers and 3-methyl butene-1 with alhpa olefin of 4～8 carbon atoms.But this process is very ineffective to the transparency that improves poly-third sheet material.

In order to overcome the above problems, from a large amount of results, find, if the vinyl naphthenic polymkeric substance that contains 6 carbon atoms is at least added in the crystalline p p sheet, then can improve the toughness of poly-third sheet material and transparency and unlikely cause bleach, variety of issues such as transparency reduction and scent of.

The present invention relates to and contain 0.05ppm～1%(weight) crystalline p p sheet of the vinyl cycloalkanes polymkeric substance of (by vinyl cycloalkanes unit).

Crystalline polypropylene sheet material flexible proposed by the invention and transparency aspect the best.Specific term " sheet material " (sheet) refers to the thin slice that thickness obtains with general extrinsion pressing greatly between 0.1～3 millimeter.

The amount of adding vinyl cycloalkanes polymkeric substance is not very strict, but for the variation of the original physical property of polypropylene is minimized, reasonable a kind of method is: vinyl cycloalkanes polymkeric substance addition can decide according to nucleating effect, as long as obtain the nucleating effect of needs, will reduce its addition as much as possible.Therefore, we advise that the content (calculating with vinyl cycloalkanes unit) of vinyl cycloalkanes polymkeric substance arrives 1%(weight at 0.05ppm), but better then be 0.5 to 5,000ppm(weight).

The vinyl naphthenic compounds that the present invention uses should contain 6 carbon atoms at least, comprising the vinyl tetramethylene, and the vinyl pentamethylene, vinyl-3-methylcyclopentane, vinyl cyclohexane, vinyl-2-methylcyclohexane, vinyl-3-methylcyclohexane and vinyl norbornene alkane.The compound that has 8 or more carbon atom in the above-mentioned vinyl naphthenic compounds is preferentially selected for use in the present invention.

The crystalline polypropylene mixture that contains above-mentioned vinyl cycloalkanes polymkeric substance can prepare as follows.

(1) in the presence of Ziegler-Natta catalyst, vinyl cycloalkanes polymerization reaction take place (carbon atom quantity is at least 6), then, the equal polymerization of propylene or with other alpha-olefin copolymer.

(2) polymkeric substance that obtains from (1) is mixed with alfon, or mix with the propylene alpha-olefin copolymer.

(3) vinyl cycloalkanes (containing more than the six carbon atom) polymkeric substance mixes with alfon or mixes with the propylene alpha-olefin copolymer.

(2) and the propene polymer of using in (3) can with known polymer blending, as ethylene/propylene rubber (EP rubber), weighting material, as mica, talcum etc.Available known hybrid technology, for example, the Brabender machine, roller press, or forcing machine mixes.Secondly, also can in polypropylene composite, add some common compounds as required, as anti degradant, lubricant, static inhibitor, release agent etc.

Make with Z-N (type) catalyzer and to contain at least 6 carbon atom vinyl cycloalkanes polyreactions and can obtain isotactic polymer.The titanium trichloride catalyst of being sold by Toyo Stauffer and Marubeni Solvay company limited etc. relatively is fit to the present invention's use.Secondly, also be suitable for the present invention attached to the catalyzer on the magnesium compound, this magnesium compound was mentioned Japanese patent application No59916/82 and 133408/80 li.

Contain 0.05ppm to 1%(weight) the crystalline polypropylene mixture of vinyl cycloalkanes polymkeric substance (by vinyl cycloalkanes unit), by using general extrinsion pressing to be processed into sheet material, and can not bleach, transparency reduces and produce smell, and good toughness and transparency is arranged.

According to the moldable all styles of that is configured as of crystalline polypropylene sheet material that the present invention produces, representative instance is as follows.

This sheet material can be used for the food that solidifies that soybean makes, clam, and oyster, the packaging vessel of fruit jelly etc., this container adopts vacuum forming; Can be used for food, the packaging vessel of PTP etc., this packing adopts pressure forming; Be applicable to the packing such as the penholder of stationery, the front cover of book; Be applicable to electrical equipment, as VTR magnetictape cartridge case, floppy disc etc.

Following example compares detailed narration to the present invention, but does not limit the present invention.

Limiting viscosity [η], the measuring method of melting index and mist degree thereof is as follows.

(1) limiting viscosity [η]

Under 135 ℃ of temperature, use the Wu Bailuo viscometer, be that solvent is measured limiting viscosity with the 1,2,3,4-tetralin.

(2) melting index

Measure according to the JISK6758 method.

(3) interior mist degree

Interior mist degree is measured according to the ASTMD1003 mode.In the mensuration process, this sample is soaked in the influence of eliminating sample surfaces in the Glass tubing that fills dimethyl phthalate.

Embodiment 1

(A) preparation of organo-magnesium compound:

To be used for Grignard reagent synthetic 12 gram magnesium thin slices and put one 1 liter flask into, this flask has agitator, reflux condensing tube, drop-burette.With gas in the argon replaces flask, in flask, import 250 milliliters of di-n-butyl ethers, put 62 milliliters of n-butyl chlorides (mole ratio of n-butyl chloride and magnesium is 1.2: 1) in the drop-burette.Remain on and make it begin reaction in 50 ℃ the flask by n-butyl chloride being splashed into temperature.In 2 hour time, dripped n-butyl chloride.After this, continue reaction 2 hours, make di-n-butyl ether dissolving normal-butyl chlorination magnesium.The strength of solution of normal-butyl chlorination magnesium is 1.45 mol.

(B) preparation of magnesium compound:

With 55 milliliters of silicon tetrachlorides of 112 milliliters of dilution with toluene, resulting solution (mole ratio of magnesium and silicon is 1: 1) splashes in the normal-butyl chlorination magnesium solution that method obtains described in top (A).Under 20 ℃ of temperature, drip this solution three hours, generate a kind of white depositions.

Then, be reflected at and proceed 1 hour under the same temperature.After reaction was finished, the standing and reacting mixture was removed supernatant liquid, and the throw out that obtains is cleaned with normal heptane, can obtain 65 gram solid phase prods after drying in the vacuum.

(C) preparation of solid catalyst:

After in having 200 milliliters flask of agitator and thermometer, carrying out air displacement, as solvent, add 30 milliliters of titanium tetrachlorides simultaneously, 12.85 gram phenol, reheat to 50 ℃ with 70 milliliters-chlorobenzene.There is hydrogen chloride gas to overflow in the reaction process.Reaction is carried out 1 hour until finishing.Getting 1 milliliter of reaction mixture sample analyzes.In the infrared absorption spectrum of sample, the absorption of the stretching vibration of the OH base of phenol is not observed.Obtain average group like this and become Ti(OC ₆H ₅) _0.5Cl _3.5Liquid titanium compound.

Add 15 milliliters of ethyl benzoates in this reaction soln, 5 grams resulting solid phase prod in (B), the mixture heating up to 120 that obtains ℃ thus.

Catalyzed reaction stirs and to carry out 1 hour under 120 ℃, allows reaction mixture sat, and the liquid separation on upper strata is come out.

Subsequently, in throw out, add 50 milliliters of normal heptanes, under 90 ℃, reacted while stirring 5 minutes, place for some time, remove supernatant liquid.After repeating this step 5 time, stop to clean.

Remaining throw out is carried out vacuum-drying obtain 3.4 gram solid catalysts.Titanium atom content is 2.6%(weight in the solid catalyst).

(D) polyreaction of vinyl cyclohexane

Employed flask injects 100 milliliters of dehydrations and purified normal heptane with argon replaces air wherein in this bottle, 1.95 gram triethyl aluminums, 675 milligrams of right-ethyl anisates, 6 solid catalysts that in (C), obtain of gram, then, with the mixture heating up to 50 that generates ℃.

Then add 50 milliliters of vinyl cyclohexane, polyreaction 15 minutes.

Subsequently, the polymer syrup that obtains is cleaned four times with 200 milliliters of normal heptanes, remove unreacted vinyl cyclohexane, the cocatalyst triethyl aluminum of adding and right-ethyl anisate.From the thick slurry thing of activity, remove normal heptane (by the method for underpressure distillation), obtain the active catalyst that 7.8 grams contain the polyvinyl eyclohexane powder.Polyvinyl eyclohexane content in this powder is 0.3 gram/every gram solid catalyst.

Restrain the polymerizing catalyst that contains polyvinyl eyclohexane that obtains above with 1.06,0.75 gram triethyl aluminum, 0.237 gram p-methylbenzoic acid and 1500 milliliters of normal heptanes, polypropylene in one 5 liters stainless steel still, pressure is 6 kg/cm (gauge pressures), 70 ℃ of temperature, hydrogen concentration are the 1.5%(volumes), polymerization reaction time is 40 minutes.

Reaction finishes, and adds 50 milliliters of propyl carbinols and stops polyreaction.Take out polymer syrup, from solution, obtain polymer powder with filtration method.With 500 milliliter of 1 equivalent hydrochloric acid flushing polymer powder, become neutrality with washed with methanol to powder then.Dry weighing can obtain 840 gram dry powder.

Every gram solid catalyst polymeric propylene amount is 1030 grams, and [η] is 1.93 deciliter/gram.

The calcium stearate that in containing the mixture of multipolymer that 85% melting index is 2.0 alfon and 15% method for preparing, adds 0.1 part (weight), 0.2 part (weight) as " BHT " (2.6-two-tertiary butyl hydroxytoluene) of stablizer, and adds 0.05 part Irganox101 again

(trade name: oxidation inhibitor (producing) by Ciba-Geigy AG, four-[methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic salt] methane).They are mixed in the Henschel mixing machine, more this mixture is transported to forcing machine (40 millimeters of diameters) and is processed into the material grain.

Above-mentioned material grain melts under 280 ℃ of temperature, by sheet extruder (40 millimeters of diameters) extrusion moulding, cools off with the cooling drum under 35 ℃ of temperature then and solidifies, and is shaped to a kind of refrigerative sheet material of 0.5 mm thick at last.

Subsequently, this refrigerative sheet material is immersed in 23 ℃ of water under the temperature 15 days, does not see muddiness.

Case of comparative examples 1

This example is not used polyvinyl eyclohexane, only is the calcium stearate (by weight) of 0.1 part of adding in 2.0 the alfon toward melting index, 0.2 part " BHT ", 0.05 part Irganox101

(by weight), reaction generates mixture, by condition mixing, the granulation identical with example 1, be molded as sheet material.

By the sheet material physicals comparison array of the sheet material physicals of the method moulding in the example 1 and reference examples 1 in table 1.

Table 1

The tension force transparency

Mist degree in the absolute transmittance of Young's modulus

MD＊ TD＊＊ （%） （%）

(kg/cm) (kg/cm)

Example 1 sheet material 7,900 7,600 89 20

Reference examples 1 sheet material 6,200 6,300 90 34

Explain: * MD: the direction of extrusion.

* TD: direction is vertical with the direction of extruding.

Embodiment 2-5

In a flask clean, import 650 milliliters of anhydrous pure normal heptanes successively, 94 mmole diethylaluminum chlorides, the titanium trichloride catalyst that 27 grams are sold by " Marubeni Solvay " company limited with the argon gas purge.Reaction mixture is heated to 60 ℃, adds 150 milliliters of vinyl cyclohexane again, polyreaction 150 minutes, the every gram titanous chloride of result obtains containing the catalyzer of 4.20 gram polymeric vinyl cyclohexane.

Use 42.3 grams to contain the catalyzer of vinyl cyclohexane polymer, 180 gram diethylaluminum chloride and 150 liters of normal heptanes carry out propylene polymerization in 300 liters of stainless steel stills, pressure is 10 kilograms/flat centimetre gauge pressure, 60 ℃ of temperature, logical hydrogen amount is the 6.0%(volume), polyreaction 5 hours.After polymerization process is finished, add 30 liters of propyl carbinols and stop polyreaction, carry out deliming and handle, from solvent, obtain polymer powder by filtering at last.

The powder for drying weighing, its weight is 29.5 kilograms, and the amount that every gram titanium trichloride catalyst obtains polypropylene is 3620 grams.[η] is 1.85 deciliter/gram.

The content of the vinyl cyclohexane in the copolymer powder is 1160ppm(weight).

Make like this multipolymer by shown in the table 2 with the homo-polypropylene with 2.0 melting index carry out mixing, with the tablets press of 65 mm dias finish mix of mixture.In the course of processing, can add stablizer, it comprises the BHT of 0.2 part (by weight), the Irganox1010 of the calcium stearate of 0.05 part (by weight) and 0.05 part (by weight).

These material grains melt extrude with the forcing machine of 65 millimeters of diameters under 280 ℃ of temperature, are that 35 ℃ cooling drum makes its cooling and typing with temperature then, obtain the sheet material of 0.5 mm thick at last.

Reference examples 2

Be used in the same quadrat method described in the example 2, homo-polypropylene (melting index=2) extruder grain with 2 li uses of example is processed into sheet material then.

Reference examples 3

Except that the compound that in the homo-polypropylene of reference examples 2, adds in the example 2, also add right-tertiary butyl benzoic acid aluminium salt (PTBBA-Al) of 0.1PHR.With the method identical with example 2, these mixture pelletings that obtains, molding is processed into sheet material then.

Reference examples 4

In a flask clean, import 20 milliliters of anhydrous pure normal heptanes successively, 8.0 mmole diethylaluminum chlorides, the titanium trichloride catalyst that 1.17 grams are sold by " Marubeni Solvay " company limited with the argon gas purge.With the mixture heating up to 60 that makes ℃, add 3-methyl butene-1 gas subsequently in the gas phase part, carry out 5 hours polyreactions.The polymers obtained amount of every gram titanium trichloride catalyst is 0.31 gram.

Use above-mentioned identical catalyzer, and diethylaluminum chloride, by with example 1 in identical method with propylene polymerization, obtain containing the polypropylene of the 3-methyl butene-1 of 400ppm.

Add with example 1 in after the employed same additives, 97 parts of (by weight) melting index are homo-polypropylene and 3 parts (by weight) of 2 to make polyacrylic mixture as stated above, use the method identical with example 1 to be processed into sheet material.

The characteristic of the physical property of embodiment 2 to 5 sheet materials and reference examples 2 to 4 sheet materials is listed at table 2.With other sheet material contrast, the toughness and the transparency of sheet material of the present invention are best.

Table 2

Ratio of mixture tension force transparency

Mist degree in the homo-polypropylene multipolymer Young's modulus

（%） （%） MD TD （%）

(kg/cm) (kg/cm)

1. reference examples 2 100-6,400 6,500 33

2. example 2 99 1 7,300 7,300 30

3. example 3 97 3 7,600 7,500 25

4. example 4 90 10 7,900 7,600 20

5. example 5 70 30 8,200 8,100 16

6. reference examples 3 100-7,400 7,300 30

7. reference examples 4 97 3 6,600 6,500 33

Embodiment 6

In a flask clean, import 650 milliliters of anhydrous pure normal heptanes successively with the argon gas purge, 94 mmole diethylaluminum chlorides, 27 gram titanium trichloride catalysts (selling) by Marubeni Solvay company limited, mixture heating up to 60 ℃, add 40 milliliters of vinyl cyclohexane subsequently, polyreaction obtained a kind of catalyzer after 40 minutes, in this catalyzer, every gram titanium trichloride catalyst polyreaction 1.02 gram vinyl cyclohexane.

With the above-mentioned vinyl cyclohexane polymer catalyzer that contains of 45.7 grams, 180 gram diethylaluminum chlorides, 150 liters of normal heptanes, in one 300 liters stainless steel seal pot with the then polymerization of propylene, ethylene random, its polymerizing condition is an ethylene concentration 1.5%(volume), pressure is 4 kg/cm (gauge pressures), 50 ℃ of temperature, hydrogen concentration 1.5%(volume) polyreaction is after 5 hours, add 30 liters of propyl carbinols and stop polyreaction, carry out deashing simultaneously simultaneously, last, by filtering, from solvent, obtain polymer powder.

Dried polymer powder weight is 54.7 kilograms, and every gram solids containing titanium catalyzer institute polymeric propylene amount is 2350 grams.[η] is 2.12 deciliter/gram.

It is 434ppm that the polymer weight that the content of vinyl cyclohexane is generated according to the per unit titanium trichloride catalyst in the copolymer powder is calculated.With diameter is that 65 millimeters tablets presss are processed into the material grain to this multipolymer, in this process, adds the BHT of 0.2 part (by weight), the calcium stearate stablizer of 0.05 part (by weight) and the Irganox1010 of 0.05 part (by weight)

These material grains are melted under 280 ℃ of resin temperatures and extrude, and are 65 millimeters sheet extruder moulding with diameter, make its cooling and shaping become the sheet material of 0.5 mm thick with cooling drum.In the course of processing, do not find rust staining on the cylinder and the phenomenon of being fuming.In temperature is 23 ℃, and relative humidity is under 50% the situation, to deposit 60 days, and the situation that additive is separated out does not take place sheet material.

Reference examples 5

With reference to the method for embodiment 6 same additive being joined melting index is that the content of therein ethylene is 2%(weight in atactic propene/ethylene copolymer of 2).According to embodiment 6 modes synthetics is molded as sheet material.

The physicals that embodiment 6 and reference examples 5 make sheet material is listed in the table 3.

Table 3

The tension force transparency

Mist degree in the Young's modulus

MD TD （%）

(kg/cm) (kg/cm)

1. example 6 7,400 7,400 15

2. reference examples 5 5,300 5,200 25

With reference to specific embodiment the present invention is described in detail, apparent, to those skilled in the art that, in flesh and blood of the present invention and processing range, can make various forms of changes and improvements.

Claims (3)

1, the crystalline polypropylene extrusion molding sheet material that contains vinyl cycloalkanes polymkeric substance is characterized in that this ethene cycloalkanes contains at least 6 carbon atoms, and the content of vinyl cycloalkanes polymkeric substance in the sheet material (by vinyl cycloalkanes unit) is 0.05ppm to 1% (weight).

2, crystalline polypropylene extrusion molding sheet material according to claim 1, the content (by vinyl cycloalkanes unit) that it is characterized in that vinyl cycloalkanes polymkeric substance is 0.5-5,000ppm(weight).

3, crystalline polypropylene extrusion molding sheet material according to claim 1, it is characterized in that described vinyl cycloalkanes is selected from: vinyl tetramethylene, vinyl pentamethylene, vinyl-3-methylcyclopentane, vinyl cyclohexane, vinyl-2-methylcyclohexane, vinyl-3-methylcyclohexane and vinyl norbornene alkane.