CN109153159A - Polyolefin composition for rotational molding - Google Patents
Polyolefin composition for rotational molding Download PDFInfo
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- CN109153159A CN109153159A CN201780030367.XA CN201780030367A CN109153159A CN 109153159 A CN109153159 A CN 109153159A CN 201780030367 A CN201780030367 A CN 201780030367A CN 109153159 A CN109153159 A CN 109153159A
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- polyolefin
- weight
- stabilized
- polyolefin composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
Abstract
The present invention relates to a kind of polyolefin compositions for rotational molding, the polyolefin composition includes stabilized polyolefin and not stabilized polyolefin, wherein the average particle size of not stabilized polyolefin is 10 microns to 250 microns, and melt flow index range is 0.001g/10 minutes to 15.0g/10 minutes (at 190 DEG C, 5kg) or 0.0002g/10min to 3.0g/10 minutes (at 190 DEG C, 2.16kg).The polyolefin composition also includes metallic stearate.
Description
Technical field
The present invention relates to the polyolefin compositions for rotational molding.
Background technique
Due to cost of investment height, by injection molding, extrusion or blow molding manufacture polyolefin hollow product, especially such as ice holds
The massive articles such as device, chest, water tank, industrial tank, kayak, surfboard may be infeasible.The suitable manufacture of this product
Technique is rotational molding (rotational molding) comprising 4 steps: being loaded, heating, cooling and demoulding.
Primary raw material for rotational molding includes fluoropolymer resin, stabilizer, pigment and additive.In rotational molding mistake
These components are mixed before journey.It is mixed with two ways, i.e., dry-mixed and melt blending.It is more preferable due to moulding article
Colour consistency and better appearance, melt blending be preferred for the process.Currently, for the most extensive of rotational molding
The fluoropolymer resin used is polyethylene, because it provides equilibrium response in terms of mechanical performance, processability and cost.
Due to certain limitations of polyethylene performance in rotational molding application (rotomolded application), introduce
Other polymer are to improve required performance.For example, multi-layer rotating molds tank, outer layer is mainly made of polyethylene, internal layer by
Polar polymer is made, such as nylon or ethylene-vinyl alcohol copolymer, with fuel-resistant permeability, so that fuel is to environment
Discharge reduce.In some applications, rotation molded articles must be filled in its cavity with polyurethane foam, to provide necessity
Function, including mitigate weight, brisk (buoyancy), dimensional integrity, heat-insulated etc..
Due to its inertia and non-polar nature, polyethylene itself cannot be effectively combined with other polymer.When product passes through
When going through certain situations, the poor bonding between them can cause serious problem.In the application of cooler/ice chest, outer wall and interior
Layer is made of the polyethylene of rotational molding, and middle layer is filled with polyurethane thermal barrier.When box exposes at high temperature, example
Such as in sunlight, thermal weld and/or flame treatment, polyethylene outer wall separates the polyurethane foam with filling, leads to its size
Integrality is lost, this will affect the appearance of box.
US4,440,899 disclose a kind of surfboard, the polyethylene outer wall made of roational molding and are filled in
Its internal polyurethane foam composition.If surfboard is damaged at polyethylene outer wall, polyethylene outer wall and polyurethane foam
Between poor adhesiveness may make water penetration in entire polyethylene and polyurethane interface, cause damage to be expanded in surfboard
It dissipates.However, water only occurs at the point of damage and seeps if having excellent bonds between polyethylene outer wall and polyurethane foam
Thoroughly.
In order to enhance through the bond properties between the rotational molding polyethylene prepared and polyurethane foam, develop
Chemically and physically technology.In physical technique, thick polyethylene powders expand before cooling step as second of injection (shot)
It dissipates in the cavity of rotation molded articles.The thick polyethylene powders being attached on the inside polyethylene wall of heat provide rougher interior
Surface allows preferably to adhere to polyurethane foam.However, adhesion strength is heavily dependent on the distribution of thick PE.In general, logical
It crosses the technology and has been obtained for the poor variation bonded to very strong polyurethane foam.The technology is quite high-cost side
Method because have to using a large amount of thick polyethylene, such as thick polyethylene amount based on the weight of polyethylene in first time injection
It is about 20 weight %.In addition, diffusing step is also labor-intensive.
2006000770 A1 of WO, which is disclosed, carries out rotational molding work by using the polyethylene powders of corona treatment
Skill improves the bonding between polyethylene wall and polyurethane foam.Functional group on polyethylene surface increases polyethylene and poly- ammonia
Bonding between ester foam.However, corona treatment is a kind of high cost process, and for polyurethane foam bonding,
The quality of the polyethylene powders of corona treatment depends on polyvinyl resin and its additive packet and corona treatment item
Part.
US 4,440,899 discloses a kind of polyolefin composition for rotational molding, with improved to polyurethane
The bonding of foam.The composition includes slightly stabilized polyolefin or not stabilized polyolefin and exists in stabilizer
Under stabilized polyolefin, the stabilizer such as 2- hydroxyl -4- n-octyloxy-benzophenone and octadecyl -3- (3,5- bis- uncles
Butyl -4- hydroxy phenyl) propionic ester.At the process conditions, the slightly stabilized polyolefin or not stabilized polyene
Hydrocarbon is capable of forming oxide group, so as to improve the bonding with polyurethane.
US 3,974,114 discloses the polyolefin composition for rotational molding, and it includes polyolefin, stabilizer and choosings
From the C of calcium, lithium, magnesium, barium, cadmium and aluminium salt8-C18Fatty acid salt.Preferably, stabilizer is 2,6- di-t-butyl-paracresol
(DBPC) and dilauryl thiodipropionate (dilauryl thiopropionate, DLTDP).
8,357,324 B2 of US discloses a kind of method for producing polyethylene hollow product, and this method is using one kind or more
A variety of NO- acyl group hindered amines are as stabilizer, to reduce the heating time of rotational molding, to obtain the good machine of hollow product
Tool performance.The method includes one or more NO- acyl group hindered amines are added into polyethylene, which is filled into mold
In, the mold is heated to 280 DEG C or more in an oven, rotates mold around at least two axis, it is cold while still rotating
But mold opens it, and takes out resulting hollow product.
Although having attempted to improve the property of the composition for rotational molding as described above and moulding technology, deposit
It is controlled in some problems, such as with the quality of polyurethane foam bonding, includes containing the stabilized of pigment in polyolefin composition
In the case where polyolefin and not stabilized polyolefin without pigment, the unsatisfactory appearance of hollow product is (such as
Surface pinholes) and colour consistency.In certain circumstances, it may be necessary to more work steps with match stabilize polyolefin and
Color between not stabilized polyolefin.
Summary of the invention
The present invention relates to a kind of polyolefin compositions for rotational molding, and it includes stabilized polyolefin
(stabilized polyolefin) and not stabilized polyolefin (unstabilized polyolefin), wherein unstable
Granularity (particle size) range of the polyolefin of change is 10 microns to 250 microns, and melt flow index range is
0.001g/10min to 15.0g/10min (at 190 DEG C, 5kg) or 0.0002g/10min to 3.0g/10min (at 190 DEG C,
2.16kg).Polyolefin composition also includes metallic stearate (metal stearate).
The object of the present invention is to provide a kind of polyolefin compositions for rotational molding with multiple technologies advantage.By
Rotomolded product made of polyolefin composition according to the present invention and other materials such as polyurethane foam, nylon etc. have
Good bonding, and there is good exterior surface appearance, i.e. color difference on surface and pin hole is less.In addition, being used for rotational molding
The temperature of polyolefin composition according to the present invention is lower, and with average particle size and melt flow index beyond according to the present invention
The polyolefin composition comprising not stabilized polyolefin for limiting range is compared, and resulting rotomolded product still has quite
Stretched bonded performance.
Detailed description of the invention
Fig. 1 shows that the outer surface of the rotation molded articles made of polyolefin composition according to the present invention (is attached to
The surface of mold) and inner surface (surface for being attached to the air in mold) decaying be totally reflected Fourier Transform Infrared Spectroscopy
(ATR-FTIR spectra)。
Fig. 2 show indicate polyolefin composition in not stabilized polyethylene amount with by polyolefin according to the present invention
The figure of relationship between the value of chromatism (Δ E) of rotation molded articles made of composition.
Specific embodiment
Following details describes specification of the invention, it is no intended to limit the scope of the invention in any way.
According to the present invention, for the polyolefin composition of rotational molding include stabilized polyolefin and it is not stabilized gather
Alkene.
According to the present invention, the mean particle size range of not stabilized polyolefin is 10 microns to 250 microns, and melt flows refer to
Number ranges are 0.001 g/10min to 15.0g/10min (at 19 DEG C, 5kg) or 0.0002g/10min to 3.0g/10min (
190 DEG C, 2.16kg).In accordance with the present invention it is preferred that the mean particle size range of not stabilized polyolefin is 50 microns to 250 micro-
Rice, more preferable 100 microns to 250 microns.
The technical advantage of not stabilized polyolefin according to the present invention with selected average particle size is, when they are with powder
When the mixing of last form and storage, stabilize and do not stabilize without segregation (segregation) between polyolefin, and with use
It is compared with the not stabilized polyolefin beyond the average particle size according to the present invention for limiting range, obtained rotational molding
Product has surface pinholes seldom or the good appearance of needleless hole surface.In addition, the advantages of this selected average particle size, exists
It is avoided in it and color matching step (color matching step) is carried out to not stabilized polyolefin and stabilized polyolefin
Necessity.According to the present invention, the not stabilized polyolefin without pigment or colorant can be with the stabilized polyene of coloring
Hydrocarbon mixing, and formed with good appearance and the rotomolded product without stone effect (stone effect).[stone effect is
Lead to uneven color and bad order on the surface for the rotomolded product that colourless not stabilized polyolefin appears in coloring
The phenomenon that.] due to not needing additional pigment or colorant for not stabilizing polyolefin, polyolefin composition of the invention mentions
The saving of cost is supplied.From test result as can be seen that the average particle size of the not stabilized polyolefin more than 250 microns can draw
Play the very big uneven distribution for changing pin hole on (high variation) and surface of big pin hole, pinhole size.It is using
The polyolefin composition for stabilizing polyolefin and the not stabilized polyolefin without pigment or colorant comprising coloring
In the case of, also observe stone effect.Preferably, the average particle size of not stabilized polyolefin should from 100 microns but less
In 250 microns, to obtain excellent rotomolded product.
According to the present invention, the melt flow index range of not stabilized polyolefin be preferably 0.001g/10min extremely
5.0g/10min (at 19 DEG C, 5kg) or 0.0002g/10min to 1.0g/10min (at 190 DEG C, 2.16kg), melt flows refer to
Number ranges are more preferably 0.00l g/10min to 3.0g/10min (at 190 DEG C, 5kg) or 0.0002g/10min to 0.6g/
10min (at 190 DEG C, 2.16kg).
The technical advantage of not stabilized polyolefin with selected melt flow index is resulting rotomolded product
With with the good bonding such as other materials such as polyurethane foam, nylon.This is because the melt of not stabilized polyolefin
Flow index is no more than 15.0g/10min (at 190 DEG C, 5kg) or is no more than 3.0g/10min (at 190 DEG C, 2.16kg), with tool
There is the inner surface rougher compared to offer higher than the not stabilized polyolefin of the melt flow index of selected melt flow index
(surface for being attached to other materials) leads to the more preferable bonding with other materials.Melt flow index is less than 0.001g/10min
(at 190 DEG C, 5kg) or the not stabilized polyolefin for being less than 0.0002g/10min (at 190 DEG C, 2.16kg) will be in rotating moulds
More pin holes are generated on the surface of molding product.In addition, it is difficult to supply.
According to the present invention, the fusing point of not stabilized polyolefin is at least 4 DEG C higher than stabilized polyolefin.This generates rotation
The mainly inner surface (surface for being attached to other materials) comprising not stabilized polyolefin of moulding article and main comprising surely
Surely the outer surface (surface for being attached to mold) for the polyolefin changed.Therefore, resulting rotomolded product has with target material
Strong bonding, and also have by the high intensity and durability of the stabilizer generation in stabilisation polyolefin.
According to the present invention, the amount of not stabilized polyolefin be the 0.01 weight % based on polyolefin composition total weight extremely
15 weight %, preferably 0.01 weight % are to 10 weight %, more preferable 0.01 weight % to 6 weight %.With with higher amount not
Stabilize polyolefin rotomolded product compare, have a selected amount of rotomolded product for not stabilizing polyolefin without or
Slightly color difference.In addition, the not stabilized polyolefin of higher amount will lead to more pin holes presented on the outer surface, bigger
The very big variation (high variation) of pinhole size and pinhole size distribution.
According to the present invention, stabilized polyolefin includes polyolefin and stabilizer.
According to the present invention, stabilizer is organosulfur compound, phenolic compound, organic phosphorus compound, hindered amine compound
Or their mixture；The organic phosphorus compound is organic phosphate or ester (organophosphate), organic phosphite
(organophosphonite)。
, according to the invention it is preferred to stabilizer be phenolic compound, organic phosphite, hindered amine compound or they
Mixture.
The example of phenolic compound stabilizer according to the present invention is (3- (3, the 5- di-t-butyl -4- hydroxyls of pentaerythrite four
Phenyl) propionic ester (Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-hydroxyphenyl)
Propionate), three (3,5- di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester (Tris (3,5-di-tert-butyl-4-
Hydroxybenzyl)-isocyanurate), tocopherol) etc..
The example of organic phosphorus compound stabilizer according to the present invention is bis- (2,4- di-t-butyl -6- aminomethyl phenyl) ethyls
Phosphate (Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphate) or three (2,4- di-t-butyls
Phenyl) phosphite (Tris (2,4-ditert-butylphenyl) phosphite).
The example of hindered amine compound stabilizer according to the present invention is poly- (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidines
Ethyl alcohol-friendship -1, 4- succinic acid) (Poly (4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-
Alt-1,4-butanedioic acid)), poly- [[6- [(1,1,3,3- tetramethylbutyl) amino]-s- triazine -2,4- diyl] -
[(2,2,6,6- tetramethyl -4- piperidyl) imino group]-hexa-methylene-[(2,2,6,6- tetramethyl -4- piperidyl) imino group])
(Poly [[6- [(1,1,3,3-tetramethylbutyl) amino]-s-triazine-2,4-diyl]-[(2,2,6,6-
Tetramethyl-4-piperidyl) imino]-hexamethylene- [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]) or No. CAS chemical substance etc. for 192268-64-7.
According to the present invention, the total weight based on stabilized polyolefin, the amount of stabilizer are 0.005 weight % to 0.2 weight
Measure %.
According to the present invention, stabilized polyolefin also includes pigment.
By rotational molding, even if polyolefin composition according to the present invention is used without any pigment or colorant not
Stabilized polyolefin will not generate or almost without color difference.
According to the present invention, based on the total weight of polyolefin composition, the amount of stabilized polyolefin be 85 weight % extremely
99.9 weight %, preferably 90 weight % are to 99.99 weight %, and more preferable 94 weight % to 99.99 weight %.
The amount one of not stabilized polyolefin is provided and used as previously described using stabilized polyolefin with above-mentioned amount
The technical advantage of sample.
According to the present invention, stabilized polyolefin and not stabilized polyolefin can be identical or different polyolefins
Type, preferably identical polyolefin type.
According to the present invention, stabilized polyolefin and not stabilized polyolefin are polyethylene, polypropylene or theirs is mixed
Close object.
Stabilized polyolefin according to the present invention can be prepared by melt blending (melt blending).It can pass through
Twin-screw extrusion machining mixing polyolefin, additive, pigment or colorant and stabilizer.
It according to the present invention, also include metallic stearate for the polyolefin composition of rotational molding.Metallic stearate
It is zinc stearate, calcium stearate, magnesium stearate, aluminum stearate or their mixture.
According to the present invention, based on the total weight of polyolefin composition, the amount of metallic stearate be 0.004 weight % extremely
0.04 weight %.
Polyolefin composition in the presence of metallic stearate according to the present invention can provide technical advantage.When at certain
When being molded under one peak internal air temperature (peak internal air temperature, PIAT), be not present metallic hard
It is compared when resin acid salt by the layered product that polyolefin composition obtains, is obtained in the presence of metallic stearate by polyolefin composition
The layered product obtained shows less pin hole.It in other words, can be at lower PIAT by existing in metallic stearate
It is lower that the layered product with needleless hole surface is obtained using polyolefin composition.
It according to the present invention, can be by super mixer with 500 rpms for the polyolefin composition of rotational molding
The speed of (rpm) to 1500 rpms (rpm) was prepared through 2 minutes to 8 minutes, to obtain good compatible polyolefin composition
Object.
As described above, the polyolefin composition according to the present invention for rotational molding have important characteristic, as component,
The amount etc. of component, this provides technical advantage to rotation molded articles as described above.However, being used for the polyolefin of rotational molding
Composition is not limited to the scope of the present invention.In fact, in addition to shown and described herein other than those, from the foregoing description,
Various modifications of the invention will become obvious to those skilled in the art.These modifications, which are also intended to, falls into the present invention
In the range of.
It is according to an embodiment of the invention, but the range that is not intended to be limiting of the invention below.
The analysis of the oxidation of rotomolded product during rotational molding of experiment 1
Polyolefin composition of the invention shows the excellent bonds to polyurethane foam, this is because in the moulding process phase
Between not stabilized polyolefin oxidation.The oxidation can be totally reflected Fourier transformation infrared spectrometer by decaying
(Attenuated Total Reflectance Fourier Transform Infrared Spectrometer, ATR-
FTIR it) characterizes.
According to ATR-FTIR as a result, discovery oxidation occurs mainly in the inner surface for the rotomolded product for being exposed to air
On.By observing 1715cm-1Carbonyl at wave number, which stretches peak, can determine polyethylene oxide, as shown in Figure 1.
2 bonding test of experiment and rotational molding time
It is tested by measuring tensile strength according to ASTM D1623 viscous between rotomolded product and polyurethane foam
It closes.Rotational molding sample can be prepared as follows:
Sample 1 is molded by using the polyolefin composition comprising stabilized polyethylene powders, the polyethylene
The average particle size of powder is 300 microns and TmIt is 124 DEG C.
Sample 2 is gathered by using the stabilized polyethylene powders comprising 95 weight % and the not stabilized of 5 weight %
The polyolefin composition of ethylene powder is molded, and the average particle size of the stabilized polyethylene powders is 300 microns and Tm
It is 124 DEG C, and the average particle size of the not stabilized polyethylene powders is 165 microns and TmIt is 129 DEG C.
Based on the total weight of the stabilized polyethylene powders, in the polyolefin composition in sample 1 and sample 2
Stabilized polyethylene powders include the stabilizer of the phenolic compound of 0.03 weight % and the organic phosphite of 0.1 weight %
Mixture.
Inside Air Temperature is the key process parameter of heat cycles in tracking rotary moulding process.Gained rotational molding portion
The maximum temperature of the physics of part and chemical property and inner air or commonly referred to as peak internal air temperature (PIAT) close phase
It closes.
According to the present invention, tensile strength is determined as the function of PIAT.It was found that reaching tensile strength is more than for sample 1
The PIAT of 200kPa or more is higher than 238 DEG C.For sample 2, reaching the PIAT that tensile strength is more than 200kPa is about 220 DEG C.This
The result shows that, reduce the energy in rotomolding process using the rotational molding sample of polyolefin composition according to the present invention a bit
Amount consumption and heating time, and there is the bonding of improved polyurethane foam.
Test the influence of the granularity of 3 not stabilized polyolefin
In order to illustrate the technical advantage of the granularity of not stabilized polyolefin according to the present invention, prepares and researches and include
The polyolefin composition sample of not stabilized polyolefin with a variety of average particle sizes.
The sample of polyolefin composition (1-4) includes
The stabilized polyethylene of (1) 95 weight %, melt flow index be 3.5g/10min (at 190 DEG C,
2.16kg), density 0.932g/cm3, TmIt is 124 DEG C and average particle size is 300 microns.
The stabilized polyethylene includes polyethylene, pigment and stabilizer, the gross weight based on stabilized polyethylene
The organic phosphite of the amount hindered amine compound comprising 0.1 weight % and 0.015 weight %, and
(2) with the not stabilized polyethylene of a variety of average particle sizes, as shown in table 1.The not stabilized polyethylene
Melt flow index be 0.030g/10min (at 190 DEG C, 5kg), and TmIt is 129 DEG C.PIAT in rotomolding process is set
It is scheduled on 180 DEG C.
According in table 1 as a result, come the polyene of the self-contained not stabilized polyethylene for being 670 microns with average particle size
The moulding article (sample 4) of compositions of hydrocarbons shows stone effect on the outer surface of sample.
Influence of the average particle size of the not stabilized polyolefin of table 1 to the outer surface beauty of rotational molding sample
When considering the pin hole on surface, carry out the self-contained not stabilized poly- second for being greater than 250 microns with average particle size
The molded samples of the polyolefin of alkene (sample 3 and sample 4, average particle size are respectively 320 microns and 670 microns) are shown can not
The appearance of receiving, i.e., the very big variation (high of the pinhole size distribution presented in biggish pinhole size and outer surface
variation)。
From result above it may be concluded that the average particle size of not stabilized polyethylene according to the present invention give it is excellent
Different and acceptable appearance.
Test the influence of the melt flow index (MFI) of 4 not stabilized polyolefin
In order to illustrate the technical advantage of the melt flow index of not stabilized polyolefin according to the present invention, preparation has
Two kinds of polyolefin composition samples of the not stabilized polyolefin of a variety of melt flow indexes, and studied as follows,
Two kinds of polyolefin composition samples contain the stabilized polyethylene of 95 weight %, the stabilized polyethylene packet
Include polyethylene and stabilizer.Stabilizer is the hindered amine compound of 0.1 weight % of the total weight based on stabilized polyethylene
With the mixture of the organic phosphite of 0.015 weight %.The melt flow index of the stabilized polyethylene is 3.5g/
10min (at 190 DEG C, 2.16kg), density 0.932g/cm3, TmFor 124 DEG C and average particle size is 300 microns.
For polyolefin composition sample 1, by the not stabilized polyethylene of the stabilized polyethylene and 5 weight %
Mixing, the average particle size of the not stabilized polyethylene are 165 microns, and melt flow index is 7.5g/10min (190
DEG C, 2.16kg) and TmIt is 131 DEG C.
For polyolefin composition sample 2, by the not stabilized polyethylene of the stabilized polyethylene and 5 weight %
Mixing, the average particle size of the not stabilized polyethylene are 165 microns, and melt flow index is 0.03g/10min (190
DEG C, 5.0kg) and TmIt is 129 DEG C.
Said polyolefins composition sample is mixed by using super mixer.
Two kinds of polyolefin composition samples are subjected to rotational molding at a variety of PIAT.It was found that sample 1 by ATR-FTIR
The minimum temperature at the carbonyl functional group peak that technology detects is 4 DEG C higher than the minimum temperature of sample 2.In addition, the inner surface of sample 1
(being attached in polyurethane foam) is smooth, and the inner surface of sample 2 is coarse.Known rough surface allows and substrate
More preferable bonding.It is lower than sample 2 according to the tensile strength of the bonding display sample 1 of the polyurethane foam samples of ASTM D1623 test
Tensile strength.
From result (as shown in table 2) it may be concluded that with the unstable of melt flow index according to the present invention
Polyolefin composition provides the advantage that 1) during rotational molding when reduction energy consumption and heating in the presence of the polyethylene of change
Between and 2) compared with using the not stabilized polyethylene with higher melt flow index, rotation molded articles, which have, to be improved
The bonding and good mechanical performance with polyurethane foam.
Inner surface appearance and polyethylene wall of the melt flow index of the not stabilized polyethylene of table 2 to rotation molded articles
The influence of tensile strength between polyurethane foam.
* it is similar to the light of the inner surface of the product made of polyolefin composition when not stabilized polyolefin is not present
Sliding appearance
The critical PIAT of * is the minimum PIAT for starting to be detected by ATR-FTIR technology in carbonyl peak.
Average tensile strength when the critical PIAT of * *
Test the influence of the amount of 5 not stabilized polyolefin
In order to illustrate the technical advantage for the amount for not stabilizing polyethylene in polyolefin composition according to the present invention, preparation tool
There are many polyolefin composition samples for the not stabilized polyolefin measured, to study the shadow to products appearance such as surface pinholes
It rings, it is as follows,
The sample (1-3) of polyolefin composition includes
The stabilized polyethylene of (1) 95 weight %, melt flow index be 3.5g/10min (at 190 DEG C,
2.16kg), density 0.932g/cm3, TmFor 124 DEG C and average particle size is 300 microns.
The stabilized polyethylene includes polyethylene, pigment and stabilizer blend, and it includes based on stabilized poly-
The phenolic compound of 0.03 weight % of the total weight of ethylene and the organic phosphite of 0.1 weight %, and
(2) with the not stabilized polyethylene of various amounts as shown in table 3.The not stabilized polyethylene is averaged
Granularity is 165 microns, and melt flow index is 0.030g/10min (at 190 DEG C, 5kg) and TmIt is 129 DEG C.
PIAT in the rotomolding process of polymer sample (1-3) is set in 190 DEG C.As a result such as table 3 and Fig. 2 institute
Show.
Influence of the amount of the not stabilized polyethylene of table 3 to the exterior surface appearance of rotomolded product
It can be seen that the not stabilized polyethylene (sample beyond the scope of this invention in 20 weight % from result (table 3)
Product 3) in the presence of, the rotation molded articles from polyolefin composition show unacceptable exterior surface appearance, i.e. pin hole
The pinhole size distribution greatly variation (high variation) that size is larger, pin hole quantity mostly and on outer surface is presented.
Later, the test of influence of the not stabilized polyolefin to color sample is carried out to the rotational molding sample of acquisition.
Color difference (Δ E) at 2.3 is set as to the upper limit of color tolerance.
According to the present invention, color difference can be prosperous by desk-top spectrophotometer (Benchtop Spectrophotometer)
Spy vertical (Hunterlab) measurement, and can be calculated by following formula:
Wherein, Δ E is color difference
Δ L is luminance difference
Δ a is Red Green difference
Δ b is the difference of Yellow-Blue
It is found from result (Fig. 2), there is the not stabilized polyethylene more than 6 weight %, (sample 2 and sample 3 are distinguished
Not stabilized polyethylene with 10 weight % and 20 weight %) in the case where, the rotational molding from polyolefin composition
Sample shows the value of chromatism greater than 2.3.In other words, every color difference of sample can be observed.
As set forth above, it is possible to draw a conclusion, the amount of not stabilized polyethylene according to the present invention be 0.01 weight % extremely
15 weight % obtain the few and small acceptable appearance of pin hole.In addition, in suitable not stabilized polyethylene, due to low
Value of chromatism, 0.01 weight % to 6 weight % allows to obtain excellent and acceptable appearance.
Test influence of 6 metallic stearates to rotomolded product surface pinholes
In order to illustrate technical advantage of the metallic stearate in polyolefin composition according to the present invention, to metal tristearin
The Effect study of hydrochlorate is as follows:
The sample (1-3) of polyolefin composition includes
(1) stabilized polyethylene, melt flow index are 3.5g/10min (at 190 DEG C, 2.16kg), and density is
0.932g/cm3, TmFor 124 DEG C and average particle size particle size is 300 microns.Stabilized polyethylene includes polyethylene, pigment and steady
Determine agent, the stabilizer is the phenolic compound and 0.1 weight of 0.03 weight % of the total weight based on stabilized polyethylene
Measure the mixture of the organophosphorus ester of %.
(2) the not stabilized polyethylene of various amounts as shown in table 4.The melt flows of this not stabilized polyethylene
Index is 0.030g/10min (at 190 DEG C, 5.0kg) and TmIt is 129 DEG C, and
(3) optionally, the calcium stearate of 0.01 weight % of the total weight based on polyolefin composition shown in table 4.
From the results of view, when compared with the product from the polyethylene composition there is no calcium stearate, from presence
The rotomolded product of the polyethylene composition of calcium stearate shows lower PIAT and less pin hole.This causes rotating
The reduction of time and energy consumption in moulding process.
Table 4 is for the component of the polyolefin composition of test and the PIAT of display needleless hole surface
* calcium stearate is mixed with not stabilized polyethylene.
Specific embodiment
Best mode of the invention is as disclosed in detailed description.
Claims (15)
1. a kind of polyolefin composition for rotational molding, the polyolefin composition include
(a) stabilized polyolefin, and
(b) not stabilized polyolefin
Wherein the mean particle size range of the not stabilized polyolefin is 10 microns to 250 microns, and melt flow index model
Enclose for 0.001g/10 minutes to 15.0g/10 minutes (at 90 DEG C, 5kg) or 0.0002g/10 minutes to 3.0g/10 minutes (
190 DEG C, 2.16kg).
2. polyolefin composition according to claim 1, wherein the mean particle size range of the not stabilized polyolefin
It is preferred that 50 microns to 250 microns, more preferable 100 microns to 250 microns.
3. polyolefin composition according to claim 1, wherein the melt flow index of the not stabilized polyolefin
Preferred 0.001g/10 minutes to 5.0g/10 minutes of range (at 190 DEG C, 5kg) or 0.0002g/10 minutes to 1.0g/10 minutes
(at 190 DEG C, 2.16kg), more preferable 0.001g/10 minutes to 3.0g/10 minutes of melt flow index range (at 190 DEG C,
5kg) or 0.0002g/10 minutes to 0.6g/10 minutes (at 190 DEG C, 2.16kg).
4. polyolefin composition according to claim 1, wherein the fusing point of the not stabilized polyolefin is more steady than described
Surely at least 4 DEG C of the polyolefin height changed.
5. polyolefin composition according to any one of claim 1 to 4, wherein based on the total of the polyolefin composition
Weight, the amount of the not stabilized polyolefin are 0.01 weight % to 15 weight %, preferably 0.01 weight % to 10 weight %,
And more preferable 0.01 weight % to 6 weight %.
6. polyolefin composition according to claim 1, wherein the stabilized polyolefin includes polyolefin and stabilization
Agent.
7. polyolefin composition according to claim 1 or 6, wherein the stabilized polyolefin also includes pigment.
8. polyolefin composition according to claim 6, wherein the total weight based on the stabilized polyolefin, described
The amount of stabilizer is 0.005 weight % to 0.2 weight %.
9. the polyolefin composition according to claim 6 or 8, wherein the stabilizer is organosulfur compound, phenol generalization
Close object, organic phosphorus compound, hindered amine compound or their mixture, the organic phosphorus compound be organic phosphate or
Ester, organic phosphite, the preferred phenolic compound of the stabilizer, organic phosphite, hindered amine compound or theirs is mixed
Close object.
10. according to claim 1, polyolefin composition described in 6 or 7, wherein the total weight based on the polyolefin composition,
The amount of the stabilized polyolefin is 85 weight % to 99.99 weight %, preferably 90 weight % to 99.99 weight %, and more
It is preferred that 94 weight % to 99.99 weight %.
11. polyolefin composition according to any one of the preceding claims, wherein the stabilized polyolefin and institute
Stating not stabilized polyolefin is polyethylene, polypropylene or their mixture.
12. polyolefin composition according to any one of the preceding claims, wherein the polyolefin composition also includes
Metallic stearate.
13. polyolefin composition according to claim 12, wherein the metallic stearate is zinc stearate, stearic acid
Calcium, magnesium stearate, aluminum stearate or their mixture.
14. polyolefin composition according to claim 12 or 13, wherein the total weight based on the polyolefin composition,
The amount of the metallic stearate is 0.004 weight % to 0.04 weight %.
15. polyolefin composition according to any one of the preceding claims, wherein the polyolefin composition passes through height
Fast mixer was prepared with 500 rpms to 1500 rpms of speed through 2 minutes to 8 minutes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TH1601001538A TH181002A (en) | 2016-03-18 | Polyolefin compositions for rotational molding | |
| TH1601001538 | 2016-03-18 | ||
| PCT/TH2017/000020 WO2017160243A1 (en) | 2016-03-18 | 2017-03-16 | Polyolefin composition for rotational molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109153159A true CN109153159A (en) | 2019-01-04 |
Family
ID=59071048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780030367.XA Pending CN109153159A (en) | 2016-03-18 | 2017-03-16 | Polyolefin composition for rotational molding |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN109153159A (en) |
| PH (1) | PH12018501945A1 (en) |
| SG (1) | SG11201807667TA (en) |
| WO (1) | WO2017160243A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115052734A (en) * | 2020-02-17 | 2022-09-13 | 诺瓦化学品(国际)股份有限公司 | Rotational moulding composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3166167A1 (en) * | 2020-02-17 | 2021-08-26 | Nova Chemicals Corporation | Rotomolding composition |
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| GB0414372D0 (en) | 2004-06-26 | 2004-07-28 | Clarehill Plastics Ltd | Rotational moulding product and process |
| JP5718316B2 (en) | 2009-04-21 | 2015-05-13 | ビーエーエスエフ、パフォーマンス、プロダクツ、エルエルシー | Rotomold process for polyethylene materials |
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2017
- 2017-03-16 CN CN201780030367.XA patent/CN109153159A/en active Pending
- 2017-03-16 WO PCT/TH2017/000020 patent/WO2017160243A1/en active Application Filing
- 2017-03-16 SG SG11201807667TA patent/SG11201807667TA/en unknown
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2018
- 2018-09-11 PH PH12018501945A patent/PH12018501945A1/en unknown
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|---|---|---|---|---|
| US5783611A (en) * | 1996-05-24 | 1998-07-21 | Millennium Petrochemicals Inc. | Composition and process for rotational molding foamed articles |
| CN1688654A (en) * | 2002-10-01 | 2005-10-26 | 埃克森美孚化学专利公司 | Polyethylene compositions for rotational molding |
| CN1788048A (en) * | 2003-05-12 | 2006-06-14 | 陶氏环球技术公司 | Polymer composition and process to manufacture high molecular weight-high density polyethylene and film therefrom |
| CN102227468A (en) * | 2008-10-02 | 2011-10-26 | 道达尔石油化学产品研究弗吕公司 | Method for additivating polymer in rotomoulding applications |
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| CN115052734A (en) * | 2020-02-17 | 2022-09-13 | 诺瓦化学品(国际)股份有限公司 | Rotational moulding composition |
Also Published As
| Publication number | Publication date |
|---|---|
| SG11201807667TA (en) | 2018-10-30 |
| WO2017160243A1 (en) | 2017-09-21 |
| PH12018501945A1 (en) | 2019-06-17 |
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