CN85101716A - Ethylene polymer blend reaches by its container that makes - Google Patents

Abstract

Disclose and contained 75-90 weight % line style high density ethylene polymer (density at least 0.94 grams per milliliter, melt-flow index was less than 0.5 gram/10 minutes) and the polymeric blends of 10-25 weight % low density ethylene polymer (density is less than 0.93 grams per milliliter, and melt-flow index restrains/10 minutes less than 2.0).This mixture has a kind of combined physical performance and environmental stress crack resistance energy.This performance makes it well suited in making the blow-molded container that is used to pack solution washing agent composition again.

Description

Ethylene polymer blend reaches by its container that makes

Fluid container by the blow molding of line style high density ethylene polymer is easy to comprise distilled water with suitable cost production and as many types of liquid products that moisture hypochlorite bleaching, vinegar, lubricating oil and other container have obtained extensively general admitting.Such container is also as some types of liquid Betengent product of packing.Yet, because the tendency that the detergent product of many types makes container stress crack occur quickens, so use this container package detergent product to be subjected to some restriction.Stress crack is because the crackle outward appearance of bluring on the container shows, and this outward appearance is not conform to ideal aesthetically concerning the ultimate consumer.Under the few cases, stress crack can cause content to release from container.The anti-stress cracking resistance of line style high density ethylene resin can be by these resins and other polymkeric substance, as if isoprene-isobutylene rubber, ethylene-propylene copolymer rubber reaches other mixing and answers and improve.Yet the mixture that obtains has reduced intensity and hardness is not suitable for many packing purposes.

For above-mentioned reasons, on technology, must advance to change to contain line style high density ethylene polymer resin combination and improve the performance of anti-environmental stress crack.Improved resin combination like this except the performance of anti-environmental stress crack with improvement, also will require to keep the gross of the polyvinyl physicals that meets the requirements of employed line style height in producing blow-molded container at present.

The invention provides a kind of two kinds of dissimilar polyvinyl complete molten mixtures of equilibrium property of concrete satisfaction, make it be suitable for highlightedly making container again by blow molding process.The character of this complete molten mixture is listed in following:

Property value

Tensile yield point, pound/cun ²At least 2000

Ultimate elongation, pound/cun ²At least 3800

Young's modulus, pound/cun ²At least 45000

Modulus in flexure, pound/cun ²At least 65000

Break elongation, % is at least about 650

The melt-flow index gram/minute is less than about 2.0

Mixture of the present invention contains at least a line style high density ethylene polymer of about 75-90 weight % and about at least a linear, low density ethene polymers of 10-25 weight %, and said ethene polymers is formed in about 98 weight % of the total polymer that contains in the said mixture at least under further condition.

Mixture of the present invention contains one or more line style high density ethylene polymers.Various line style high-density contained in mixture are at least about 0.94 grams per milliliter, about during melt-flow index restrains/10 fens less than 0.5, wherein incite somebody to action the ethene of polymerization 98 mol % at least, polymerized therein any comonomer is a kind of α-monoene footpath that contains about 3-12 carbon atom.Such line style high density ethylene polymer is known and was reported in the prior art and can have been bought by many manufacturers in industry.This line style high density ethylene polymer is at the like chrome catalysts of some metal catalyst, for example is carried on the CrO on the silica-alumina carriers ₃, and Ziegler-natta catalyst, for example TiCl that uses together with some aluminum alkyl catalyst ₃When existing, and when having the optional α that contains 4-12 carbon atom-monoene footpath copolymerization to exist, make by making vinyl polymerization.Condition by suitable controlled polymerization comprises: temperature, pressure, the concentration of comonomer, and the concentration of the telogen as hydrogen density that obtains requiring in the polymkeric substance and the melt-flow index that closes needs.Preferred its density of its density ethylene polymer of line style high density ethylene polymer is at least about 0.95 grams per milliliter.Particularly preferred density polymer is at least about 0.96 grams per milliliter.

The linear, low density ethene polymers density that is comprised in the mixture of the present invention is preferably in about 0.91 to about 0.92 grams per milliliter scope, particularly about 0.92 grams per milliliter about 0.91 to about 0.93 grams per milliliter scope.This line style, the melt-flow index of low density ethylene polymer be less than about 2.0, preferably less than about 1.0 grams/10 minutes.Closing the melt-flow index that it is desirable to the line style high density ethylene polymer that contains in this melt-flow index and the mixture is close.These polymkeric substance are multipolymers of ethene, this copolymer polymerization about 2-6, be preferably α-monoolefine that about 4-6 mol % contains 3-12 the carbon atom of having an appointment, wherein the monomeric surplus of institute's polymeric is an ethene.Used linear, low density ethene polymers contains long linear chain and has the relative short side chain along its whole length and linear chain connection that is controlled quantity among the present invention.These side chains, or " side chain " be concrete α-monoolefine short and that use during according to the preparation polymkeric substance, contains 1-10 the carbon atom of having an appointment.This linear, low density ethene polymers is structurally different with the low density ethylene polymer that the polymerization that is caused by the high pressure radical makes, and also has only few long-chain branch even it has.

This linear, low density ethene polymers can have been bought by multiple commercial source industrial.This polymkeric substance makes ethene make with containing a kind of α-monoolefine copolymerization of 3-12 the carbon atom of having an appointment by when having some metal catalyst for the used general type of preparation line style high density ethylene polymer discussed above to exist.The polymerizing condition that uses when it prepares is slightly had any different and is used slightly improved catalyzer.Make ethene and butene-1 generation copolymerization a kind of the comprising with a fluidization bed process for preparing the technology of this polymkeric substance in vapour phase.Owing to carry out the restriction that this polymerization produced in vapour phase, the ethene polymers that makes with this method is limited to ethene and 1-Butylene copolymer.By operating in holding the agent system, the copolymerization physical efficiency is made by the comonomer that contains the α-monoolefine that reaches as high as 12 carbon atoms.The preferred linear, low density ethene polymers that comprises in mixture of the present invention is an ethylene copolymer, and wherein polymerization has the comonomer of a kind of α-monoolefine that contains 6-12 carbon atom at least, and randomly also contains the butene-1 of copolymerization therein.

The polyvinyl ratio of line style high density ethylene polymer and linear, low density can be according to multiple consideration, be included in the line style high density ethylene polymer and the polyvinyl accurate composition of linear, low density that contain in the mixture, by the profile of the container of mixture blow molding, and the composition of in the container that makes, packing and slightly changing.In order to reach the performance of the anti-environmental stress crack that significantly improves mixture of the present invention, mixture should contain at least about 10 weight % linear, low density ethene polymerss.In order to obtain necessary blow-molded container intensity to withstand this container suffered load in industry is used, this mixture should contain 75 weight % line style high density ethylene polymers at least.For most of general objects purposes, this mixture should contain have an appointment 80-90 weight % line style high density ethylene polymer and about 10-20 weight % linear, low density ethene polymers.

When preparation pure mixture of the present invention, preferably use the line style high density ethylene polymer of single variety and the linear, low density ethene polymers of single variety, have selected two kinds of polyvinyl ratios to satisfy the character standard of mixture requirement.When the preparation blow-molded container, as known in existing skill, the pruning material of certain percentage is recovered and must recycles to reach low production cost.Collect and prune waste material, and be milled to small particle size, mix with pure polymer then with the preparation mixture.This recycled materials is known as " material later ".As long as keep some preventive measures, later material can mix with purified polymer in reality of the present invention.Particularly, pure ethene polymers should be done like this with contained material ratio later, make in the limits that the ratio of line style high density ethylene polymer that polymeric blends used in the container of blow molding contains and the poly-mixture of linear, low density ethene formerly stipulates, and stipulate that further two kinds of specified ethene polymerss are formed in 98% weight of the polymeric blends that uses in the blow molding operation at least.Any a spot of polymkeric substance that does not belong to the definition of the line style high density ethylene polymer of above defined and linear, low density ethene polymers should be restricted to other his type ethene polymers.

Polymkeric substance of the present invention except polymerization composition described above, can also contain a small amount of other compositions that use with the ethene polymers that uses in the blowing production that coexists usually.Particularly, mixture of the present invention can contain antioxidant, stablizer, and pigment, tinting material, and common the use in this polymer compound has the similar substance of function to provide it to be used to.

Polymkeric substance of the present invention will satisfy the Schwellenwert for some character that is listed in the table 1, and be preferred value in many cases.

Table 1

Character Schwellenwert preferred value

Tensile yield point, pound/cun ²2,000 3,200

Ultimate elongation, pound/cun ²3,800 4,200

Bullet limit modulus, pound/cun ²45,000 72,000

Modulus in flexure, pound/cun ²65,000 82,000

Melt-flow index restrains/10 minutes less than 2.0 less than 0.5

Tension values, modulus value and melt-flow index value are to be measured by the ASTM method of using in ethene polymers technology, additional disclosure, and melt-flow index is by ASTM1238-70, condition E, i.e. standard load melt-flow index pH-value determination pH.

Embodiment 1

A

The industrial available density that the polymeric blends of the present invention that makes contains 80 and 90 parts of weight is that 0.953 grams per milliliter and melt-flow index are 0.3 line style high density ethylene polymer, and 10 and 20 parts of industrial available density of weight are that 0.92 grams per milliliter and melt-flow index are 1.0 the poly-and thing of linear, low density ethene.It is poly-and method is obtained and be considered to contain octene-1 as comonomer that this linear, low density ethene polymers is considered to a kind of molten night.These two kinds of polyvinyl particles that adopt rotate in drum to make a kind of uniform physical mixture, then by a prepare burden extrusion machine and being granulated.Thing in contrast is for the recording process process also is to be extruded separately to the line style high density ethylene polymer and the linear, low density ethene polymers of the independent batch of material of influence of physical properties.

Used extrusion machine is a length/diameter than a kind of 30 millimeters Moder ZSK-30 twin-screw extruders of 27.Extruding condition is:

Processing parameter

Temperature, ℃

Segmentation 1 170

2 200

3 200

4 204

Wire drawing die head 5 206

Fusion 210

Screw speed, rotations per minute 300

Pressure, pound/cun ²550

Torque, % 60-80

Productive rate, Pounds Per Hour 22-25

B

The mold pressing test agent is for measuring physicals.List in table 2 according to the value that test records.

Table 2

Tested performance compound, high density polyethylene(HDPE)/LLDPE

(test method) 10,0/0 90,/10 80,/20 100/0

Melt-flow index restrains/10 minutes 0.103 0.082 0.091 0.568

（ASTMD-1238）

Modulus in flexure, pound/cun ²159,000 127,000 72,000 38,000

（ASTMD-747）

Tensile property,

（ASTMD-638）

Young's modulus, pound/cun ²100,000 90,000 82,000 28,000

Tensile yield point, pound/cun ²3,300 2,900 3,200 1,500

The elongation at yield rate, % 7.7 9.5 8.3 13.9

Ultimate elongation, pound/cun ²4,600 4,600 4,200 4,400

Elongation limit, % 664 704 715 900

Molecular weight

The glue post sees through chromatographic analysis

（GPC）Mw 203，360 215，920 208，400

Mn 19，010 19，070 30，060

Mz 834，920 1238，000 768，700

Dn 10.72 13.31 6.94

Tested performance compound, high density polyethylene(HDPE)/LLDPE

(test method) 10,0/0 90,/10 80,/20 100/0 calorifics

Performance

Differential scanning calorimeter Ti Tp Tf Ti Tp Tf Ti T PTi

（DSC）

Fusion, ℃

For the first time heat 64 140 149 72 131 149 60 130 138

Reheating 65 134 145 65 132 146 56 125 131

Crystallization, ℃

For the first time heat 123 116 64 123 116 53 112 106 41

Mw=weight-average molecular weight Ti=starting temperature

Mn=number-average molecular weight Tp=peak temperature

Mz=Z average molecular weight Tf=outlet temperature

Dc＝Mw/Mn

The physicals of 90/10 and 80/20 mixture is highly suitable for to preparing the resin system that blow-molded container is used.The modulus in flexure value of 80/20 mixture is because uncertain testing error and very low.If redeterminate this value, survey the modulus in flexure value and will substantially exceed 1000,000 pounds/cun ²

Two kinds of polyvinyl performance numerical value that comprise in mixture that the supplier announces are listed in table 3.

Table 3

Melt-flow index restrains/10 minutes line style high density polyethylene(HDPE) LLDPE

（ASTMD-1238） 0.3 1.0

Density, gram/cubic centimetre 0.953 0.920

（ASTMD-792）

Modulus in flexure, pound/cun ²120,000 44,000

（ASTMD-747） （ASTMD-790）

1% secant modulus, pound/cun ²115,000 30,000

（ASTMD-638）

C

80/20 mixture of A portion and line style high density ethylene polymer use a single cavity extrusion blow machine to be blow molded into to have 28 ounces of volumes, and are used to pack the container in the type transverse section, ellipse garden of Parson board ammoniacal liquor.About 50 grams of each receptacle.Used processing condition are listed in table 4.

Table 4

Extruding

Temperature, °F

Segmentation 1 370

2 400

3 400

4 400

5 400

6 400

7 420

8 420

9 420

10 420

Screw speed, per minute rotating speed 27

Blowing

Cycle period, second

Last blowing 10

Whole 16*

* all cycle period is 16 seconds to the container by the blowing of line style high density ethylene polymer resin, is 15 seconds to ethylene polymer blend.

By measuring the comparison intensity that container under the bin stock condition has been measured in its maximum load resistance to compression with ASTM method D-2659-67.The value of high-density polyethylene container is 25 pounds, and the value of 80/20 mixture container is 24 pounds.Thereby found out that the intensity of container of the present invention when bin stock is identical with the prior art container basically.This result has remarkable ratio accordingly aspect the low value of the container of line style high density polymer blowing at the container by the blowing of linear, low density ethene polymers, is surprising and is not expected to.

D

Use a kind of special testing sequence to detect in C portion the performance of the anti-environmental stress crack of two containers that make by two blow-molded containers of 80/20 mixture preparation and by the line style high density ethylene polymer.In this test, each container is equipped with about three ounces of patented product fluids that contain the ortho-water solution vessel of a kind of anion sulfoacid salt surfactant of a kind of negatively charged ion.Be selected as this product of content in the test, be known in by causing the serious stress be full of cracks in the blow-molded container of line style high polymer system.Seal this container and remain on 140 °F.Check the container of charging every day, and be enough to the tangible first liquid of record when releasing evidence, finish this test when this container chaps to.

Leakage has taken place in 2 days in the container that is made by the line style high density ethylene polymer one after on-test.Leakage has taken place in after test 20 days of second container by the line style high density ethylene polymer.The container none in 50 days that is made by ethylene polymer blend of the present invention leaks.By a kind of contain a kind of so significant environmental stress crack resistance that 80% weight line style high density ethylene polymer makes can improvement, be surprising being not expected to again.

Although described here polymeric blends and constituted this bright preferred embodiment by the blow-molded article that it is made, but the invention is not restricted to these polymeric blends and blow-molded article, under the situation of not leaving the scope of the invention of illustrating in the claims, can change therein.

Claims (15)

1, a kind of polyvinyl complete molten mixture; Said mixture contains have an appointment at least a line style height of 75-90 weight % ethene polymers and at least a linear, low density ethene polymers of about 10-25 weight %, and said ethene polymers is formed in about 98 weight % of the whole polymkeric substance that contain in the said mixture at least; The density of the every kind of high density ethylene polymer that comprises in mixture is at least about 0.94 grams per milliliter, melt-flow index restrains/10 minutes less than about 0.5, polymerization 98 mol % ethene of having an appointment at least wherein, wherein any comonomer of institute's polymeric is a kind of α-monoolefine that contains 3-12 the carbon atom of having an appointment; The every kind of linear, low density ethene polymers density that comprises in the mixture is less than about 0.93 grams per milliliter, melt-flow index restrains/10 minutes less than about 2.0, the about 2-8 mol of polymerization therein % contains the α-monoolefine of 3-12 the carbon atom of having an appointment, and polymerized therein monomeric surplus is an ethene.

2, a kind of mixture of claim 1 wherein contains have an appointment 80-90 weight % line style height ethene polymers and about 10-20 weight % linear, low density ethene polymers.

3, a kind of ethene polymers of claim 2, the contained linear, low density ethene polymers in wherein at least a the inside is that a kind of copolymerization has the ethene polymers that contains 6-12 carbon atom α-monoolefine.

4, a kind of mixture of claim 1, wherein the density of high density ethylene polymer is at least about 0.95 grams per milliliter.

5, a kind of mixture of claim 1, wherein the density of high density ethylene polymer is at least about 0.96 grams per milliliter.

6, a kind of mixture of claim 2, wherein the density of high density ethylene polymer is to about 0.95 grams per milliliter.

7, a kind of mixture of claim 2, wherein the density of high density ethylene polymer is at least about 0.96 grams per milliliter.

8, a kind of mixture of claim 3, wherein the density of high density ethylene polymer is at least about 0.95 grams per milliliter.

9, a kind of mixture of claim 3, wherein the density of high density ethylene polymer is at least about 0.96 grams per milliliter.

10, a kind of fluid container comprises a screw-like container finish part; A shoulder portion; A main part; With a bottom; Said container is made by the polyvinyl complete fused mixture of a kind of claim 1 of blowing.

11, a kind of fluid container comprises a screw-like container finish part; A shoulder portion; A main part; With a bottom; Said container is made by the polyvinyl mixture that melts that holds fully of a kind of claim 2 of blowing.

12, a kind of fluid container comprises a screw-like container finish part; A shoulder portion; A main part; With a bottom; Said container is made by the polyvinyl mixture that melts that holds fully of a kind of claim 3 of blowing.

13, a kind of closed container of packing a kind of water phase surfactant mixture therein; Said container comprises a screw-like container finish part; A shoulder portion; A main part; With a bottom; Said container is made by the polyvinyl mixture that melts that holds fully of a kind of claim 1 of blowing.

14, a kind of closed container of packing a kind of water phase surfactant mixture therein; Said container comprises a screw-like container finish part; A shoulder portion; A main part; With a bottom; Said container is made by the polyvinyl complete fused mixture of a kind of claim 2 of blowing.

15, a kind of closed container of packing a kind of water phase surfactant mixture therein; Said container comprises a screw-like container finish part; A shoulder portion; A main part; With a bottom; Said container is made by the polyvinyl complete fused mixture of a kind of claim 3 of blowing.