CN110041470A - A kind of functional olefines block copolymer antioxygen master batch and preparation method thereof - Google Patents
A kind of functional olefines block copolymer antioxygen master batch and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The invention discloses a kind of functional olefines block copolymer antioxygen master batches and preparation method thereof；The antioxygen master batch includes: 60~98 parts of olefin block copolymers, 0.01~0.5 part of initiator, 0.5~5 part of diluent, 0.5~5 part of grafted monomers, assists 0.2~5 part of grafted monomers, 0.1~0.5 part of cross-linked inhibitor, 2~40 parts of antioxidant.Olefin block copolymers and cross-linked inhibitor are mixed from main spout and are added, grafted monomers, auxiliary grafted monomers and initiator are added separately to extruder different location and participate in reaction, removing residue is vacuumized after reaction, antioxidant is added in vacuum removal back segment side spout, and implement ultrasound enhancing dispersion effect at die head, finally it is granulated.The present invention selects olefin block copolymers as matrix resin, its functionalization is made by way of reactive extrursion, then add antioxidant, and One-step production provides the anti-oxidant master batch of antipolarity, highlights its functional, stability and convenience in the application.
Description
Technical field
The invention belongs to polymer modification fields, and in particular to a kind of functional olefines block copolymer antioxygen master batch
And preparation method thereof.
Background technique
Olefin block copolymers (OBC) are that Dow Chemical Company is poly- by the new olefin of catalysis block copolymerization technology synthesis
Object is closed, it is by segment (hard section) and Gao Gongju with low co-monomer content and the crystallizable ethylene-octene of high melt temperature
Content of monomer and amorphous ethylene-octene segment (soft segment) of lower glass transition temperatures composition.Since OBC is using special
Block copolymerization technology and can break in the wrong so that it has the characteristics that significantly different with other polyolefin plastomers and elastomer
The flexible material property with resistance to heat generation conventional relationship, can significantly improve compression set performance and elastic recovery performance.By
Both there is the flexibility of plastic body and elastomer in OBC, it may have the heat resistance of high density polyethylene (HDPE), so it has the material of innovation
Expect performance.
Compared with traditional random copolymerization ethylene-octene copolymer (POE), OBC more has many unique characteristics:
Such as it can realize the improvement of elasticity with heat-resisting quantity balance, and crystallization temperature with higher, when processing, can rapid shaping；
No matter at room temperature or under high temperature, all there is preferably elasticity recovery and compressive deformation；Wearability is improved.These advantages
So that OBC becomes a kind of outstanding flexible polymer substitute, has and be more widely applied range, be not limited solely to substitute
Styrene block copolymer (SEBS, SIS and SBS), ethylene-vinyl acetate copolymer (EVA), flexible polyvinyl chloride (f-PVC),
Thermoplastic dynamic perduren (TPV), flexible polyolefin and elastomer that crosslinking may be selected etc..
Traditional POE is non-polar polymer, is frequently utilized for being used to improve the tough of material in nonpolar polyolefin system
Property, elasticity and ductility, but be used for polar material such as nylon, polyester, polycarbonate etc. engineering plastics system be used to improve
Toughness, or when for polyolefin and metal, polyolefin bonding with polar resin, it is often ineffective, it is necessary to improve its pole
Property, the means of polarity have very much, common method have chemical oxidization method, flame method, plasma modification, corona discharge method,
The surface modifying methods such as primary coat method, polishing, force chemistry and graft modification processing, there are also add the tables such as surface modifier
Face blending modification method etc., various methods have its advantage and disadvantage, and wherein graft modification method is since easy to operate, effect is prominent, warp
Often be used, when being applied to the toughening of engineering plastics or bonding with other materials by the POE of graft modification, can reduce with
Perhaps intermetallic interfacial tension improves toughness or adhesive strength to polar resin, patent of invention CN102391432B,
CN103450403A and CN104592450B etc. refers to this method.But since POE fusing point is lower, is carried out grafting and changed
When property, when being difficult to improve this inherent characteristic, be used in some occasions, for example preparing tenacity increased nylon, can significantly it drop
The use temperature and heat distortion temperature of low material, using limited.And the modified POE product of polarityization being commercialized at present, all
It is that single polarityization of only having made is handled, the effect that material improves interface binding power can only be assigned, to guarantee the anti-oxidant of material
Effect needs additional addition antioxidant in downstream when use, so increase operating procedure, and two carry out resisting due to addition
Oxygen agent is mostly powder auxiliary agent, and additive amount is extremely low, in particle shape matrix resin mixing process exist mix unevenness risk,
Make antioxidant effect that can have a greatly reduced quality.
Summary of the invention
It is anti-the object of the invention is to for overcome the deficiencies in the prior art, provide a kind of functional olefines block copolymer
Oxygen master batch, and the side for preparing this complex function polyolefin master batch that can improve polarity but also assign antioxygenic property is provided
Method.
The present invention is achieved by the following technical solutions:
The present invention provides a kind of functional olefines block copolymer antioxygen master batch, including according to parts by weight such as the following group
Point:
Preferably, the olefin block copolymers are selected from Dow Chemical Company INFUSETMOne in elastic series
Kind or several compositions.
Preferably, the initiator is selected from cumyl peroxide, dual-tert-butyl peroxy isopropyl base benzene, 2,5- bis-
Bis- (tert-butyl peroxy the base) -3- hexins of methyl -2,5-, bis- (tert-butyl peroxide) hexanes of 2,5- dimethyl -2,5-, benzoyl peroxide first
At least one in acyl, two carbonic ester of tert-butyl peroxide, tert-butyl hydroperoxide and the peroxide -2- ethylhexyl carbonate tert-butyl ester
Kind.
Preferably, the diluent is one or more of acetone, butanone, ethyl alcohol, white oil.
Preferably, the grafted monomers are maleic anhydride, dibutyl maleate, itaconic acid, citric acid, propylene
At least one of acid, methacrylic acid, glycidyl methacrylate, silane.More preferably maleic anhydride, acrylic acid,
One of glycidyl methacrylate and silane.
Preferably, the auxiliary grafted monomers be styrene, α-methylstyrene, in divinylbenzene at least
It is a kind of.
Preferably, the cross-linked inhibitor is triphenyl phosphite, caprolactam or stearic amide.
Preferably, the antioxidant is selected from Hinered phenols, phosphorous acid esters, amine, thioesters or triazines
One or more of antioxidant.
The invention further relates to a kind of preparation method of functional olefines block copolymer antioxygen master batch, the preparation method packets
Include following steps:
S1, it after mixing the olefin block copolymers, cross-linked inhibitor, is added and is reacted by main spout weight-loss metering
Extruder；
S2, by the composition containing grafted monomers and diluent, the composition containing auxiliary grafted monomers and diluent and
Composition containing initiator and diluent is dosed in extruder from three liquid injection ports respectively；
S3, it is added from the side spout of devolatilization mouth back segment through weight-loss metering after extrusion reaction and devolatilization, then by antioxidant
Into extruder, disperse in laggard excess of imports acoustic mode head through mediating；
S4, pass through application ultrasonic wave, further evenly spread to antioxidant in polymer melt, finally through die extrusion
Granulation obtains the functional olefines block copolymer antioxygen master batch.
Preferably, the extrusion temperature of the extruder is 80~220 DEG C, and revolving speed is 100~400rpm.
Preferably, the screw slenderness ratio of the extruder is greater than 48.
Preferably, the extruder is parallel dual-screw extruding machine.
Preferably, ultrasonic wave is applied by ultrasonic generator；The ultrasonic power of the ultrasonic generator
Control is controlled in 50~600W, ultrasonic frequency in 10000~30000Hz.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, the present invention completes the process of reactive extrursion, devolatilization, master batch preparation and ultrasonic disperse using one-step method, realizes
The superposition of two kinds of functions of product antipolarity and inoxidizability, and traditional preparation methods can only realize simple function；
2, present invention uses olefin block copolymers OBC as functionalized matrix resin, is carried out at polarity
After reason, it can significantly improve the use temperature of application end polar material, widen use scope, as the anti-of carrier preparation
Oxygen master batch, it is possible to reduce downstream is additionally added the step of antioxidant, and the antioxygen master batch can not only provide polarity, moreover it is possible to be made
Mixing with matrix resin more evenly makes the antioxidant effect of product more stable；
3, the present invention is needed during preparing graft using to peroxide initiator, and peroxide needs certain
Half-life period accumulation after could it is depleted, and add antioxidant be consume unreacted peroxide effective means, in this hair
In bright technique, additive amount is larger when antioxidant is used as master batch, but only needs that the mistake that do not react completely can be quenched on a small quantity
Oxide radical not only consumes free radical in this way, but also has ensured the thermo-oxidative stability of carrier itself；
4, the present invention disperses antioxidant using ultrasonic technology, improves mixed effect, so that the product of preparation is anti-oxidant
Performance is more stable.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is extruder and auxiliary device schematic diagram in the present invention；
Wherein, 1 is extruder, and 2 be screw rod, and 3 be main feeding barrel, and 4 claim for main feeding weightlessness, and 5 be main spout,
6 be grafted monomers storage tank, and 7 be the first liquid gaging system, and 8 be grafted monomers inlet, and grafted monomers storing is helped supplemented by 9
Tank, 10 be second liquid metering system, and 11 be auxiliary monomer inlet, and 12 be initiator storage tank, and 13 be third liquid meter system
System, 14 be initiator inlet, and 15 be vacuum removal system, and 16 be side feed material barrel, and 17 claim for side feed material weightlessness, and 18 be side feed
Material mouth, 19 be polymer melt, and 20 be ultrasonic generator, and 21 be energy converter, and 22 be ultrasonic probe, and 23 be extruder die head,
24 be mouth mold.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The structure of extruder used in the present invention and auxiliary device is as shown in Figure 1, be equipped with spiral shell inside extruder 1
Bar 2 is successively arranged main feeding barrel 3 along direction is squeezed out, and main feeding weightlessness claims 4, and main spout 5, three liquid feed systems take off
It waves system (i.e. vacuum removal system 15), side feed material barrel 16, side feed material weightlessness claims 17, side spout 18, ultrasonic generator
20, energy converter 21, ultrasonic probe 22 and extruder die head 23 and mouth mold 24.Wherein the first liquid feed system has grafted monomers storage
Batch can 6, the first liquid gaging system 7 and grafted monomers inlet 8 form, and second liquid feed system has auxiliary grafted monomers storage
Batch can 9, second liquid metering system 10 and auxiliary monomer inlet 11 form, and third liquid feed system is by initiator storage tank
12, third liquid gaging system 13 and initiator inlet 14 form.Polymer melt 19 is subjected in extruder die head 23
Ultrasound is squeezed out by mouth mold 24 after being uniformly dispersed and completes subsequent granulation.
Embodiment 1
First by 95 parts of olefin block copolymers INFUSETM9007 (Dow company, MI:0.5g/10min, density:
0.866g/cm-3) with 0.5 part of triphenyl phosphite extrusion is added to from main spout by weight-loss metering system after mixing
In machine；2 parts of maleic anhydride is dissolved into 3 parts of diluent butanone as grafted monomers, is added by the first liquid feed system
Enter into extruder, 1 part of α-methylstyrene is added to extruder by second liquid feed system as auxiliary grafted monomers
In, 0.2 part of cumyl peroxide is dissolved in 1 part of butanone, is added in extruder by third liquid feed system, from side
The mixture of 2.5 parts of Hinered phenols antioxidant 1098 and 2.5 part phosphite ester antioxidants 168 is added in spout, and melt is through mould
Extrusion obtains sample after implementing ultrasound when at head.
Double screw extruder draw ratio is 52 in the program, and each area's temperature setting is between 80~200 DEG C.Screw speed is
250rpm, ultrasonic power control adjust ultrasonic frequency in 15000Hz, are added, cause through fusion plastification, monomer in 200W
Grafting, devolatilization, antioxidant is added and processing steps, the sample dependence tests such as ultrasonic disperse the results are shown in Table 1.
Embodiment 2
By 30 parts of olefin block copolymers INFUSETM9100 (Dow company, MI:1g/10min, density: 0.877g/cm-3)
With 30 parts of INFUSETM9530 (Dow company, MI:5g/10min, density: 0.887g/cm-3) mixed with 0.1 part of caprolactam
It is added in extruder by weight-loss metering system from main spout after even；1 part of acrylic acid is dissolved into 0.5 as grafted monomers
It in the diluent acetone of part, is added in extruder by the first liquid feed system, 1.5 parts of divinylbenzenes connect as auxiliary
Branch monomer is added in extruder by second liquid feed system, and 0.3 part of two carbonic ester of tert-butyl peroxide is dissolved in 1 part third
It in ketone, is added in extruder by third liquid feed system, 25 parts of thioether kind antioxidants thio two is added from side spout
The mixture of propionic acid dilauryl and 15 parts of Hinered phenols antioxidants 1076 is implemented to squeeze out after ultrasound when at melt through die to obtain
Sample.
Extruder draw ratio is 56 in the program, and each area's temperature setting is between 100~220 DEG C.Screw speed is
100rpm, ultrasonic power control adjust ultrasonic frequency in 30000Hz, the dependence test result that sample is made is shown in 400W
Table 1.
Embodiment 3
By 80 parts of olefin block copolymers INFUSETM9500 (Dow company, MI:5g/10min, density: 0.877g/cm-3)
It is added in extruder by weight-loss metering system from main spout after mixing with 0.3 part of stearic amide；5 parts of methyl
Glycidyl acrylate is added to crowded as grafted monomers, 1 part of ethyl alcohol as diluent by the first liquid feed system
Out in machine, 5 parts of styrene are added in extruder as auxiliary grafted monomers by second liquid feed system, and 0.05 part 2,5-
Bis- (tert-butyl peroxide) hexanes of dimethyl -2,5- are dissolved in 1 part of ethyl alcohol, are added to extrusion by third liquid feed system
In machine, from side spout 20 parts of amine antioxidants N- cyclohexyl-N '-diphenyl-para-phenylene diamines of addition, implement when at melt through die
It is squeezed out after ultrasound and obtains sample.
Extruder draw ratio is 48 in the program, and each area's temperature setting is between 80~180 DEG C.Screw speed is
400rpm, ultrasonic power control adjust ultrasonic frequency in 10000Hz, the dependence test that sample is made the results are shown in Table in 50W
1。
Embodiment 4
By 90 parts of olefin block copolymers INFUSETM9807 (Dow company, MI:15g/10min, density: 0.866g/cm-3) be added in extruder by weight-loss metering system from main spout after mixing with 0.5 part of triphenyl phosphite；3 parts
Vinyltrimethoxysilane is added to extrusion by the first liquid feed system as grafted monomers, 3 parts of white oil diluent
In machine, 3 parts of styrene are added in extruder as auxiliary grafted monomers by second liquid feed system, 0.1 part of peroxide -2-
The ethylhexyl carbonate tert-butyl ester is dissolved in 0.5 part of white oil, is added in extruder by third liquid feed system, from side feed
10 parts of triazine kind antioxidant hexahydro -1,3,5- three [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-equal three are added in material mouth
Piperazine is implemented to squeeze out after ultrasound when at melt through die to obtain sample.
Extruder draw ratio is 60 in the program, and each area's temperature setting is between 80~220 DEG C.Screw speed is
200rpm, ultrasonic power control adjust ultrasonic frequency in 30000Hz, the dependence test result that sample is made is shown in 600W
Table 1.
Embodiment 5
By 75 parts of olefin block copolymers INFUSETM9530 (Dow company, MI:5g/10min, density: 0.887g/cm-3)
It is added in extruder by weight-loss metering system from main spout after mixing with 0.2 part of caprolactam；1 part of maleic acid
Acid anhydride is dissolved into 2 parts of diluent acetone as grafted monomers, is added in extruder by the first liquid feed system, 2 parts
Styrene is added in extruder as auxiliary grafted monomers by second liquid feed system, 0.5 part of 2,5- dimethyl -2,5-
Bis- (tert-butyl peroxy base) -3- hexins are dissolved in 1 part of acetone, are added in extruder by third liquid feed system, from side
12.5 parts of Hinered phenols antioxidant 1010 and 12.5 part phosphite ester antioxidants 626 are added in spout, when at melt through die
Extrusion obtains sample after implementing ultrasound.
Extruder draw ratio is 52 in the program, and each area's temperature setting is between 100~200 DEG C.Screw speed is
300rpm, ultrasonic power control adjust ultrasonic frequency in 20000Hz, the dependence test result that sample is made is shown in 300W
Table 1.
Comparative example 1
By 95 parts of polyolefin elastomer INFUSE in embodiment 1TM9007 are replaced with random ethylene-octene copolymer
POE, the trade mark are the ENGAGE 8150, MI:0.5g/10min of Dow company, density: 0.868g/cm-3, it is other formula and technique,
Equipment and embodiment 1 are completely the same, have obtained reference, and the dependence test of sample the results are shown in Table 1.
Comparative example 2
With embodiment 2, difference is that antioxidant is not added for each component and dosage.Technological parameter also with 2 phase of embodiment
Together, difference is non-open side feeding and implements ultrasound, and the dependence test that reference 2 is made the results are shown in Table 1.
Comparative example 3
With embodiment 3, difference is that antioxidant is not added for each component and dosage.Technological parameter also with 3 phase of embodiment
Together, difference is non-open side feeding and implements ultrasound, and the dependence test that reference 3 is made the results are shown in Table 1.
Comparative example 4
By 90 parts of olefin block copolymers INFUSETM9807 (Dow company, MI:15g/10min, density: 0.866g/cm-3) be added in extruder by weight-loss metering system from main spout after mixing with 0.5 part of triphenyl phosphite；3 parts
Vinyltrimethoxysilane is added to extrusion by the first liquid feed system as grafted monomers, 3 parts of white oil diluent
In machine, 0.1 part of peroxide -2- ethylhexyl carbonate tert-butyl ester is dissolved in 0.5 part of white oil, is added by third liquid feed system
It is reacted to squeeze out and obtain reference after devolatilization into extruder.
Extruder draw ratio is 60 in the program, and each area's temperature setting is between 80~220 DEG C.Screw speed is
200rpm, the dependence test result that sample is made such as are shown in Table 1.
Comparative example 5
By 75 parts of polyolefin elastomer INFUSE in embodiment 5TM9530 are replaced with random ethylene-butene copolymer bullet
Property body, the trade mark be Mitsui company TAFMERTMDF840, MI:3.6g/10min, density: 0.885g/cm-3, it is other formula and
Technique, equipment and embodiment 5 are completely the same, and reference is made, and the dependence test of sample the results are shown in Table 1.
Comparative example 6
Second auxiliary monomer styrene of 2 parts in embodiment 5 is not used, other formulas and technique, equipment and reality
It is completely the same to apply example 5, reference is made, the dependence test of sample the results are shown in Table 1.
Application examples 1
Respectively in Example 1 and the sample in comparative example 1 and each 20 parts of reference, nylon66 fiber (table mountain with 80 parts
Refreshing horse, EPR27) it carries out carrying out blending extrusion (extruder parameter: draw ratio 40:1, screw diameter in double screw extruder
35mm, temperature setting are 220~260 DEG C), two kinds of Toughed nylon66 sample are obtained, dependence test the results are shown in Table 2.
Application examples 2
The reference in sample and comparative example 2 in Example 2 is respectively 25 parts and 15 parts, is additionally added again in reference
The mixture for adding 6.25 parts of thioether kind antioxidant dilauryl thiodipropionates and 3.75 parts of Hinered phenols antioxidants 1076, is mixed
Hot pressing forms a film on hot press respectively after even, is then respectively placed among the aluminium foil that two layers of width is 25mm, is placed again into
Hot pressing is compound under 190 DEG C, the pressure of 2MPa on hot press, then makees T-type peel test by 2791 standard of GB/T, then by two
Kind hot-forming sample is placed in 85 DEG C, in the ageing oven of 85%RH, carries out hydrothermal aging test, dependence test the results are shown in Table 3.
Application examples 3
The reference in sample and comparative example 3 in Example 3 is respectively 5 parts and 4 parts, additional addition again in reference
1 part of amine antioxidants N- cyclohexyl-N '-diphenyl-para-phenylene diamine is applied in flame-retardant reinforced PBT as anti-oxidant and compatible
Change composite master batch to use, wherein 55 parts of PBT (Taiwan Changchun, 1100), 30 parts of glass short fine (megalith, 534A), the compound resistance of bromine antimony
15 parts of agent of combustion carries out blending extrusion (extruder parameter: draw ratio in the double screw extruder with side feeder (short fine feeding)
40:1, screw diameter 35mm, temperature setting are 200~240 DEG C), two kinds of flame-retardant reinforced PBT sample are obtained, correlated performance is tested,
And ageing properties, dependence test the results are shown in Table 4 after 5 days under the conditions of 150 DEG C for test.
Application examples 4
The sample in embodiment 4 is placed on respectively and is pressed into 420 μm of film in hot press, the reference in comparative example 4
The antioxidant with equal proportion in the embodiment 4: [β-(3,5- di-tert-butyl-hydroxy phenyl) third of hexahydro -1,3,5- three is added in sample
Acyl]-s-triazine is also disposed in is pressed into 420 μm of film in hot press after mixing, then two kinds of films are respectively placed in again
Among identical glass and backboard, retells two pieces of laminated bodies and be put into 140 DEG C of laminating machine and be laminated 20 minutes obtained laminates；So
The test-strips of a 10mm wide are marked with icking tool afterwards, to glass (peeling force of testing film sample and glass), then depth is drawn
Test peel strength is carried out according to GB/T 2791 pressure-sensitive tape, 180 ° of peeling strength test methods, then by laminate obtained
It is placed in 85 DEG C, in the ageing oven of 85%RH, carries out hydrothermal aging test.Dependence test the results are shown in Table 5.
Application examples 5
Respectively in Example 5 and comparative example 5 and the sample in comparative example 6 and each 5 parts of reference, it is applied to low cigarette
It in non-halogen flame-retardant cable formula, is formulated as follows: 20 parts of 80 parts of LLDPE (husky Bick, 218W), EVA (platform modeling, 7470M), hydrogen-oxygen
Change 160 parts of magnesium fire retardant, 5 parts of compatibilized antioxidant master batch, 130 DEG C of mixings, moulded board are made after cutting in two-roll mill
Test sample is obtained, dependence test the results are shown in Table 6.
1 embodiment of the present invention of table and comparative example try related data
| Test item | Melt index | Grafting rate |
| Test condition | 190 DEG C, 2.16kg | Chemistry titration |
| Unit | g/10min | % |
| Embodiment 1 | 0.4 | 1.2 |
| Comparative example 1 | 0.36 | 1.13 |
| Embodiment 2 | 1.2 | 0.75 |
| Comparative example 2 | 1.3 | 0.6 |
| Embodiment 3 | 4.2 | 2.4 |
| Comparative example 3 | 4.3 | 2.2 |
| Embodiment 4 | 8 | 1.4 |
| Comparative example 4 | 8.5 | 1.3 |
| Embodiment 5 | 3.2 | 0.8 |
| Comparative example 5 | 1.9 | 0.8 |
| Comparative example 6 | 4 | 0.4 |
1 test related data of application examples of the present invention of table 2
2 test related data of application examples of the present invention of table 3
3 test related data of application examples of the present invention of table 4
4 test related data of application examples of the present invention of table 5
5 test related data of application examples of the present invention of table 6
It can be seen that table 1 from the data in above table and show embodiment and comparative example functional olefines block copolymerization
The basic performance of object, from the test data of each group of comparative example and embodiment in terms of, be not much different, but due to not making in comparative example 6
With auxiliary grafted monomers, grafting efficiency is not high, and grafting rate is significantly lower than embodiment 5 and comparative example 5.
In the test data table of application examples, when table 2 illustrates to use olefin block copolymers as functionalised supports, system
Standby multifunctional mother granules are applied in PA66, and low-temperature impact resistance and heat distortion temperature will be substantially better than traditional random be total to
Polyolefin elastomer is clustered, moreover, after 1000h long-term thermo-oxidative ageing, the multi-functional mother of olefin block copolymers carrier
Influence of the grain to material property decline is obviously less than the multifunctional mother granules for using traditional POE as carrier.
As can be seen from Table 3, the functionalization antioxygen master batch that prepared by embodiment 2 is than 2 olefin block copolymers of comparative example
Graft compound antioxidant can when in use, the performance after aging is obviously dominant, showing compound antioxidant as adhering resin
There can be antioxidant and disperse non-uniform problem, and use the functionalization antioxygen master batch of one-step method of the present invention preparation, dispersion is equal
Evenness greatly improves, and antiageing effect obviously increases.
Table 4, which also illustrates, makes multifunctional mother granules prepared with embodiment 3 compound antioxygen than graft prepared by comparative example 3
When agent, in terms of the ageing test result of the flame-retardant reinforced PBT of application, and there is obvious advantage.
Table 5 is shown in functionalization antioxygen master batch and graft compound antioxidant in the comparative test for being applied to glass bonding
In, before not carrying out hydrothermal aging test, graft and antioxidant compound system the adhesive strength even ratio in comparative example 4 make
It wants high with the adhesive strength of the functional agglomerates in embodiment 4, but after progress hydrothermal aging, uses graft in comparative example 4
It is obvious with the decline of antioxidant compound system adhesive strength, and the fluctuation of measured value is larger, shows that antioxidant is at it in comparative example
The effect of middle performance is unstable, and using the adhesive strength of the functional agglomerates in embodiment 4 through the range of decrease lower after hydrothermal aging
Spend lower, and the fluctuation very little of measured value, the stability advantage of antioxidant effect are obvious.
Table 6 shows the comparison that functionalized antioxygen master batch has used different carriers to carry out and without using auxiliary grafting list
Comparison when body, when olefin block copolymers having been used to be applied to fireproofing cable material without halide as carrier as the result is shown, knot
Fruit embodies preferably elastic and more preferably heat-resisting old also superior to the polyolefin elastomer of Ethylene/Butylene type is used as carrier
Change performance；Compared with the functionalization antioxygen master batch for being not added with second comonomer, auxiliary monomer grafting, grafting efficiency and grafting have been used
Rate significantly improves, and can see in the data of application, the physical data either before aging or after aging, embodiment 5
In functionalization antioxygen master batch effect be better than the reference in comparative example 6.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of functional olefines block copolymer antioxygen master batch, which is characterized in that including following component according to parts by weight:
2. functional olefines block copolymer antioxygen master batch as described in claim 1, which is characterized in that the olefin block is total
Polymers is selected from Dow Chemical Company INFUSETMOne or more of elastic series composition.
3. functional olefines block copolymer antioxygen master batch as described in claim 1, which is characterized in that the initiator is selected from
Cumyl peroxide, dual-tert-butyl peroxy isopropyl base benzene, 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) -3- hexins, 2,5-
Bis- (tert-butyl peroxide) hexanes of dimethyl -2,5-, benzoyl peroxide, two carbonic ester of tert-butyl peroxide, t-butyl peroxy
Change at least one of hydrogen and the peroxide -2- ethylhexyl carbonate tert-butyl ester；The diluent is acetone, in butanone, ethyl alcohol, white oil
One or more.
4. functional olefines block copolymer antioxygen master batch as described in claim 1, which is characterized in that the grafted monomers are
Maleic anhydride, dibutyl maleate, itaconic acid, citric acid, acrylic acid, methacrylic acid, glycidyl methacrylate, silicon
At least one of alkane.
5. functional olefines block copolymer antioxygen master batch as described in claim 1, which is characterized in that the auxiliary grafting is single
Body is one or more of styrene, α-methylstyrene, divinylbenzene.
6. functional olefines block copolymer antioxygen master batch as described in claim 1, which is characterized in that the cross-linked inhibitor
For triphenyl phosphite, caprolactam or stearic amide；The antioxidant is selected from Hinered phenols, phosphorous acid esters, amine, sulphur
For one or more of esters or triazine kind antioxidant.
7. a kind of preparation side of the functional olefines block copolymer antioxygen master batch as described in any one of claim 1~6
Method, which is characterized in that described method includes following steps:
S1, after mixing the olefin block copolymers, cross-linked inhibitor, reactive extrursion is added by main spout weight-loss metering
Machine；
S2, by the composition containing grafted monomers and diluent, the composition containing auxiliary grafted monomers and diluent and contain
The composition of initiator and diluent is dosed in extruder from three liquid injection ports respectively；
S3, it is added to instead from the side spout of devolatilization mouth back segment through weight-loss metering after extrusion reaction and devolatilization, then by antioxidant
It answers in extruder, disperses in laggard excess of imports acoustic mode head through mediating；
S4, pass through application ultrasonic wave, further evenly spread to antioxidant in polymer melt, finally through mouth mold extruding pelletization
Obtain the functional olefines block copolymer antioxygen master batch.
8. the preparation method of functional olefines block copolymer antioxygen master batch as claimed in claim 7, which is characterized in that described
The temperature of extruder is 80~220 DEG C, and revolving speed is 100~400rpm.
9. the preparation method of functional olefines block copolymer antioxygen master batch as claimed in claim 7, which is characterized in that described
The draw ratio of the screw rod of extruder is greater than 48；The extruder is parallel dual-screw extruding machine.
10. the preparation method of functional olefines block copolymer antioxygen master batch as claimed in claim 7, which is characterized in that logical
It crosses ultrasonic generator and applies ultrasonic wave；The ultrasonic power of the ultrasonic generator is controlled in 50~600W, ultrasonic wave frequency
Rate is controlled in 10000~30000Hz.
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| CN112300328A (en) * | 2019-07-26 | 2021-02-02 | 中石化南京化工研究院有限公司 | Functionalized modified polyolefin adhesive resin and preparation method thereof |
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