CN1955220A - Polyester resin composite and polyester resin medifier and resin molding - Google Patents
Polyester resin composite and polyester resin medifier and resin molding Download PDFInfo
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- CN1955220A CN1955220A CN 200610006240 CN200610006240A CN1955220A CN 1955220 A CN1955220 A CN 1955220A CN 200610006240 CN200610006240 CN 200610006240 CN 200610006240 A CN200610006240 A CN 200610006240A CN 1955220 A CN1955220 A CN 1955220A
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Abstract
This invention is to manufacture forming products in various shapes with polyester resin. Tackifier is added into polyester resin in according to JISK7210 with melt flowing rate (MFR) under 20g/10min(table 1, condition 4). Except above-mentioned tackifier, functional high polymer preparation which can be reacts with polyester resin is also needed, especially for regenerated polyester resin.
Description
The application is dividing an application of the Chinese patent application No.02119941.8 that submitted on May 13rd, 2002.
Technical field
The present invention relates to the modified polyester and resin composition of melt viscosity, change the polyester resin modifier of vibrin melt viscosity, and by the formed resin forming article of polyester and resin composition.
Background technology
Because the melt viscosity of vibrin is very low; so in extrusion molding that does not comprise drawing process or injection molded technology; melts hangs because of deadweight from the mouth mould of extrusion shaper or the nozzle of injection molding machine, and the phenomenon that occurs hanging, for the very difficulty that is shaped.Can only be with the extrusion molding that comprises drawing process or injection molded technology or blow molding technology at this for the shaping of vibrin, can only be to be limited to film like, fibrous, container-like but the problem that occurs is the shape of these process formings.As long as comprise in other words: drawing process, according to the molecular orientation of drawing force change vibrin, melt viscosity just uprises, and the phenomenon that hangs of last note just is not easy to take place.
Nearest regeneration for the vibrin molding waste materials such as PET bottle that use, become the problem of concern, because of the thermally treating polyester resin in when regeneration lower molecular weightization that becomes, make melt viscosity become more and more lower, the problems referred to above have become more deep volt attitude.Even for example become the shaping thing, that is the vibrin shaping thing of lower molecular weightization just also, and its physical strength very deterioration that becomes also has a lot of problems in the use.
Always, in order to improve vibrin, the melt viscosity of recycled polyester resin particularly adds and has epoxy group(ing) etc. and can make polymer quantize with the functional group's of vibrin reaction resin.This method is used always.
But above-mentioned polymer quantification method quantizes that for polymer certain limit is arranged, and the problem that can not obtain sufficient melt viscosity for the extrusion molding of recycled polyester resin is particularly arranged.
Summary of the invention
The objective of the invention is to provide a kind of polyester and resin composition, this polyester and resin composition is formed by vibrin with according to the melt flow rate (MFR) (MFR) of JISK7210 table 1 condition 4 tackifier below 20g/10 divides, preferably add the tackifier of 2～100 mass parts with respect to the vibrin of 100 mass parts, under the special situation for the recycled polyester resin, preferably also add have can with the functional group's of vibrin reaction high molecular agent.These tackifier and this high molecular agent preferably recently mix with 1: 1～10: 1 quality.Also have, the functional group of this high molecular agent generally is an epoxy group(ing).
And the present invention also provides a kind of polyester resin modifier, and this polyester resin modifier contains melt flow rate (MFR) (MFR) and divides following tackifier and have the functional group's that can react with vibrin high molecular agent at 20g/10.These tackifier are the polymer alloy that forms of polypropylene and synthetic rubber preferably, and these tackifier and high molecular agent preferably recently mix with 6: 4～9: 1 quality.
The present invention also provides a kind of resin forming article, and this resin forming article is formed by above-mentioned polyester and resin composition.This resin forming article is manufactured according to extrusion molding or injection molded, and this polyester and resin composition need not to carry out predrying before shaping again, and the moisture that also need not to outgas in shaping is removed and dewatered processing, just may be extruded to be shaped or injection molded.
Below describe the present invention in detail.
Description of drawings
Fig. 1 has been to use the chart that concerns between the shearing rate of various tackifier and high molecular agent sample and the melt viscosity.
Fig. 2 has added the chart that concerns between the shearing rate of sample of various amount modifier As and the melt viscosity.
Fig. 3 is the chart that concerns that has added between the shearing rate of sample of various amount properties-correcting agent B and the melt viscosity.
Fig. 4 is the chart that concerns that has added between the forming temperature of sample of various amount modifier As and the helical length.
Fig. 5 is the chart that concerns that has added between the forming temperature of sample of various amount properties-correcting agent B and the helical length.
Embodiment
Vibrin
Vibrin of the present invention is the resulting resin of esterification of the above carboxylic acid of above polyvalent alcohol of binary and binary, such as, ethylene glycol terephthalate (PET) (hereinafter to be referred as PET), butylene terephthalate etc.
The present invention is useful for the recycled polyester resin especially.
Tackifier
Tackifier of the present invention are in order to increase the melt viscosity of vibrin.As such tackifier, will select the resin or the elastomerics of high melt viscosity for use.Following illustration is these tackifier once, as, the elastomerics of polyolefin resins such as polyethylene, polypropylene, ethylene-ethyl acrylate copolymer or elastomerics, styrene-butadiene-styrene block copolymer (SBS), vinylbenzene-polyethylene-butadiene-styrene block copolymer styrenics such as (SEBS), or above-mentioned polyolefin resin and above-mentioned styrenic elastomerics and and elastomeric polymkeric substance.As above-mentioned synthetic rubber, such as being acrylic rubber, isobutylene-isoprene copolymer, polyethylene-polypropylene rubber (EPR, EPDM), silica gel, urethanes, fluoridize class rubber, polysulfide rubber, grafting (modification) rubber, divinyl rubber, synthetic polyisoprene, neoprene, polyisoprene rubber, polyisobutylene rubber, butyl rubber, acrylonitrile-butadiene rubber, styrene butadiene rubbers (SBR), acrylonitrile-butadiene rubber (NSR), pyridine-divinyl rubber, styrene isoprene rubber, vinyl cyanide-neoprene, vinylbenzene-neoprene etc.
As the tackifier that high tackify effect is arranged is polypropylene and above-mentioned elastomeric polymer alloy.And EPR or EPDM or SBR that good intermiscibility is preferably arranged with polypropylene as above-mentioned synthetic rubber.Also have as the polymkeric substance of above-mentioned tackifier as use the recycled polyester resin, under pre-dried situation after the extrusion molding water-cooled, resin is not easy flavescence or caking.
The melt flow rate (MFR) of above-mentioned tackifier (MFR) be according to JISK7210 table 1 condition 4 (190 ℃ of test temperatures, test weight 21.18 (N)) for the measuring method of standard, be 0.5～20g/10 branch, preferred 0.5～10g/10 branch is more preferably 0.5～5g/10 branch.Above-mentioned tackifier normally add 2～100 mass parts for 100 mass parts vibrin, and preferably 3～50 mass parts are more preferably and add 10～20 mass parts.Under the situation of addition less than 2 mass parts of above-mentioned tackifier, the tackify effect is not remarkable, and the phenomenon that the rigidity of goods also has a reduction when surpassing 100 mass parts occurs.
With regard to the present invention, above-mentioned tackifier not merely are the melt viscosities that increases vibrin, also can be in order to improve its thermotolerance, and shock-resistance, dimensional stability, rigidity etc. and add.
The high molecular agent
As for the present invention, particularly resemble recycled polyester resin this lower molecular weightization, become under the low-down situation for melt viscosity, use the high molecular agent.As above-mentioned high molecular agent mainly use have can with the functional group's of vibrin reaction resin or elastomerics.
As can with the functional group of polyester material fat reaction, such as, epoxy group(ing), carboxyl, isocyanate group etc. are wherein preferably used and vibrin has the very epoxy group(ing) of hyperergy.As resin that has this functional group or elastomerics ethylene-methyl methacrylate glycidyl ester (GMA) multipolymer, ethylene-acrylic acid copolymer, ethene-ethene copolymers such as different acrylonitrile copolymer are arranged mainly, polypropylene grafted ethene copolymer with the graft copolymerization of above-mentioned ethene copolymer ethene, contain epoxy group(ing) SBS, contain the SEBS of epoxy group(ing), the EEA that contains epoxy group(ing), the SBS that contains carboxyl, the SEBS that contains carboxyl, contain the EEA of carboxyl etc., and the difference of the solubility parameter of above-mentioned high molecular agent and tackifier is preferably in 1.
The tackifier that are used for above-mentioned high molecular agent preferably select to use the tackifier of main chain of the same race.Such as being to resemble under the situation of olefines of polyethylene, EEA, EPR or EPDM-sample for tackifier, ethylene-methyl methacrylate glycidyl ester (GMA) multipolymer, ethylene-acrylic acid copolymer as the high molecular agent, ethene-olefines high molecular agent such as isocyanic acid vinyl ester copolymers are selected, for tackifier is under the situation of SBS or SEBS, the SBS that contains epoxy group(ing), the SEBS that contains epoxy group(ing), the high molecular agent that contains the SBS of carboxyl, the SBS such as SEBS that contains carboxyl or SEBS class is selected.For the addition of the above-mentioned high molecular agent of vibrin 100 mass parts 0.1～100 mass parts normally, but 0.3～50 quality height preferably is more preferably 1.0～20 mass parts.
When the addition of above-mentioned high molecular agent during in discontented 0.1 mass parts, the high molecular effect can not be given full play to the effect of dissolving mutually for tackifier, but when surpassing 100 mass parts, and this effect is not significant to be changed and become saturated.
The mixture ratio of mixed above-mentioned tackifier and above-mentioned high molecular agent 1: 1～10: 1 mass ratio preferably usually in above-mentioned vibrin.The addition that is to say the high molecular agent also lacks than tackifier, if addition is more than 1/10 of tackifier, the high molecular effect just can be brought into play fully, if but addition is the equivalent that surpasses tackifier, it is saturated that the polymer effect will become, and extrusion molding is also just hindered.
Polyester resin modifier
Can be modulated into polyester resin modifier to above-mentioned tackifier and above-mentioned high molecular agent mixing.This situation is that the mixture ratio of these tackifier and this polymeric agent is as aforementioned, 1: 1～10: 1, but preferably mix with 6: 4～9: 1 mass ratio.With regard to the best tackifier of above-mentioned properties-correcting agent is above-mentioned polypropylene and elastomeric polymkeric substance, preferably also uses EPR, EPDM, SBR as synthetic rubber.
Other compositions
As for the present invention, in order further to improve the thermotolerance of polyester and resin composition, shock-resistance, dimensional stability, rigidity etc., can add following composition, such as, styrene isoprene rubber (SIR), styrene-ethylene copolymers, poly-(alpha-methyl styrene)-polyhutadiene-(alpha-methyl styrene) multipolymer (α-MeS-B-α-MeS), poly-(alpha-methyl styrene)-polyisoprene-poly-(alpha-methyl styrene), butadiene-styrene copolymer (BS), ethylene-propylene-ethylidene multipolymer, vinyl-vinyl acetate copolymer, ethene-1-butadienecopolymer, ethylene-propylene-ethidine-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,4 hexadiene multipolymers, ethene-1-divinyl-ethidine-norbornene copolymer, ethene-1-divinyl-1,4 hexadiene multipolymer, vinyl cyanide-neoprene (NCR), vinylbenzene-neoprene resin or elastomericss such as (SCR), lime carbonate, magnesiumcarbonate, barium sulfate, calcium sulfate, calcium sulfite, calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, magnesium oxide, titanium dioxide, ferric oxide, zinc oxide, aluminum oxide, silicon-dioxide, diatomite, rhombspar, gypsum, talcum, clay, asbestos, mica, glass fibre, Calucium Silicate powder, wilkinite, white carbon black, black wood charcoal is black, iron powder, aluminium powder, feldspar, blast furnace slag, flying dust (volcanic ash), cement, the weighting agent of zirconia powder etc., fire retardant, antioxidant, antiaging agent, UV light absorber, charged preventor, crystallization promotor, whipping agent, dyestuff, the tinting material of pigment etc.Mentioned component also can be added in the modifier.
(prescription)
The blending means of mentioned component preferably dry type is mixed, and particularly the compound particles granulation of tackifier and high molecular agent, the crushed material of hybrid polyester resin in particle preferably mixes laminar crushed material, then injection molded again.
Described as preceding note for vibrin 100 mass parts of the present invention, tackifier add more than 3 mass parts, the high molecular agent is added under the above polyester and resin composition situation of 1 mass parts, even in the regeneration of the vibrin that contains moisture in the said composition or in forming technology, add water decomposition, and by degraded, this by degraded vibrin also because above-mentioned high molecular agent and by high molecular, and also because its melt viscosity of above-mentioned tackifier also by tackify, so the predrying or degassing in shaping before shaping, moisture remove etc. processing become unnecessary.
Embodiment 1 (new vibrin)
Dicarboxylic acid units is, 100 moles of % of terephthalic acid, diol units is, 98 moles of % of ethylene glycol, glycol ether 2 rubs and shows % and get, the ethylene glycol terephthalate unit is to use (PET) that accounts for 98% mole of the full component unit of repetition, in the prescription of table 1, tackifier A (new LDPE (film grade) (LDPE): MFR 4.0g/10 branch), tackifier B (reactivity-TPO: polypropylene-EPR polymkeric substance, MFR 0.69/10 minute) each self-drying type of above-mentioned tackifier mixes, use the キ ャ ピ ロ グ ラ Off of Japan smart machine society system, mouth die orifice footpath 1mm, measure 270 ℃ of temperature, measure melt viscosity under the condition of 300 seconds warm up time, and barrel temperature is 260～270 ℃, mold (mould) temperature: 25～85 ℃ of molding surface, the about 1000kgf/cm of injection pressure
2Condition under injection molded, make the plate of 175mm * 12.7mm, thickness 4mm, and reprocess this plate and make 64mm * 12.7mm, the test film of notch depth 2.54mm (JISK7110) has been measured its shock-resistance.It the results are shown in Table 1.
Table 1
| Sample No. (embodiment 1) | 1 | 2 | 3 | 4 | 5 | |
| PET (mass parts) | 100 | 100 | 100 | 100 | 100 | |
| Tackifier (mass parts) | A(LDPE) | 10 | 20 | |||
| B (reactive TPO) | 10 | 20 | ||||
| Melt viscosity | 1.22×10 2sec -1*1 | 4500 | 5800 | 6200 | 6500 | 7100 |
| 2.43×10 3sec -1*1 | 3100 | 2400 | 2800 | 2000 | 1900 | |
| The IZOD impact value *2(kj/m 2) | 2.6 | 5.4 | 6.8 | 5.2 | 6.4 | |
*1: shearing rate
*2: according to JISK7110
As shown in table 1, according to the addition of tackifier, the melt viscosity of PET (shearing rate 1.22 * 10
2Sec
-1) phenomenon that hangs does not appear when extrusion molding, and increase to that 5000 pools are above, shock-resistance also is enhanced.
Embodiment 2 (recycled polyester resin)
Use is predrying 4 hours PET bottle waste product crushed material under 150 ℃ of conditions, in the prescription of table 2, dry type mixes tackifier A, tackifier B, tackifier C (EEA, MFR 0.6g/10 branch), tackifier D (SEBS, MFR 2.3g/10 branch) injection molded and under the same condition of high molecular agent A (SBS that contains epoxy group(ing)) tackifier, high molecular agent B (styrene-grafted ethene-GMA multipolymer), high molecular agent C (ethene-GMA multipolymer) and embodiment 1, make same test film, and similarly measured rerum natura with embodiment 1.It the results are shown in Table 2.
Table 2
| Sample No. (embodiment 2) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |
| Regenerative PET (mass parts) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Tackifier (mass parts) | A(LDPE) | 14 | 13 | 7 | |||||||
| B (reactive TPO) | 14 | 14 | 1 | 7 | |||||||
| C(EEA) | 14 | 13 | 7 | ||||||||
| D(SEBS) | 14 | 1 | 7 | ||||||||
| High molecular agent (mass parts) | A (SBS that contains epoxy group(ing)) | 4 | 4 | 4 | 4 | ||||||
| B(PS-g-EGMA) | 4 | 4 | 4 | ||||||||
| C(EGMA) | 4 | 4 | |||||||||
| Tackifier: high molecular agent (recipe ratio) | 7∶2 | 7∶2 | 7∶2 | 7∶2 | 7∶2 | 7∶2 | 7∶2 | 7∶2 | 7∶2 | 7∶2 | |
| Melt viscosity (pool) | 1.22×10 2sec -1*3 | 1380 | 3240 | 4440 | 5200 | 4380 | 3460 | 4810 | 3960 | 4210 | 4100 |
| 2.43×10 3sec -1*3 | 930 | 830 | 1490 | 1500 | 1400 | 870 | 1120 | 1210 | 920 | 1080 | |
| The IZOD impact value *4(kj/m 2) | 1.4 | 7.8 | 5.1 | 5.2 | 7.0 | 5.9 | 7.6 | 5.8 | 5.6 | 6.4 | |
| The xanthochromia of (140 ℃) when dry | Have | Do not have | Do not have | Have | Have | Do not have | Have | Do not have | Do not have | ||
| Caking when dry | Have | Do not have | Do not have | Have | Have | Have | Have | Have | Do not have | ||
*3: shearing rate
*4: according to JISK7110
Even as shown in table 2, according to the addition of tackifier and high molecular agent by the lower molecular weight change the recycled polyester resin, its melt viscosity (shearing rate 1.22 * 10
2Sec
-1) also be increased, and shock-resistance is also increased substantially.Be used as the sample No.3 of the reactivity-TPO of tackifier use in addition, 4 and 10 when drying, does not have xanthochromia, caking phenomenon also do not occur.
With regard to above sample NO.1,2,3,4,6,8 and 10 change its shearing rate (Sec separately
-1), measure its melt viscosity separately then.It the results are shown in Table 3 and Fig. 1.
Table 3
| Melt viscosity (pool) | |||||||
| Sample No. (embodiment 2) | |||||||
| 1 | 2 | 3 | 4 | 6 | 8 | 10 | |
| 1.22×10 1sec -1 | 2060 | 15500 | 8490 | 7380 | 9250 | 12200 | 13520 |
| 2.43×10 1sec -1 | 1110 | 9150 | 4560 | 7350 | 4890 | 7830 | 6040 |
| 6.08×10 1sec -1 | 1160 | 4840 | 5160 | 6140 | 2320 | 5030 | 4860 |
| 1.22×10 2sec -1 | 1380 | 3240 | 4440 | 5200 | 3460 | 4810 | 4210 |
| 2.43×10 2sec -1 | 1310 | 2460 | 3540 | 4120 | 2520 | 3280 | 3680 |
| 6.08×10 2sec -1 | 1210 | 1760 | 2700 | 2830 | 1640 | 1950 | 2210 |
| 1.22×10 3sec -1 | 1100 | 1270 | 2100 | 2130 | 1230 | 1600 | 1930 |
| 2.43×10 3sec -1 | 930 | 830 | 1490 | 1500 | 870 | 1120 | 920 |
| The phenomenon that hangs (during injection molded) | Have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
As table 3 and shown in Figure 1, sample No.2 of the present invention, 3,4,6,8 and 10 shearing rate near 0 state under, compared with the sample No.1 that do not have to add regenerative PET, any sample has all shown higher melt viscosity, and the phenomenon that hangs of the front end place vibrin of the nozzle when injection molded also is prevented from.Shearing rate when also having relative extrusion molding is near 10
2Sec
-1The situation of shearing rate under, sample No.2,3,4,6,8 and 10, compared with sample No.1, any sample is all higher, and when injection molded, the phenomenon that hangs of shaping thing also is prevented from, the possibility that abnormity is shaped also can be predicted.
This that is to say sample No.2,3,4, under 6,8 and 10 the situation, when extruding according to extrusion shaper, thickness is very average, the wire molding is just obtained smoothly, under the situation of sample No.1, the thickness inequality of wire molding, thin part has just become fragment.
On the other hand, relatively the shearing rate during injection molded 10
3Sec
-1During above shearing rate, sample No.2, all near the melt viscosity of sample No.1, the formedness of injection molded also can be predicted for 3,4,6,8 and 10 melt viscosity, any sample wherein.
Embodiment 3
Mix above-mentioned tackifier A (LDPE) 72.2 quality %, tackifier D (SEBS) 5.6 quality %), high molecular agent A (SBS that contains epoxy group(ing)) 22.2 quality % modulation polyester modification agent A, remix tackifier B (the 75 quality % of reactivity-TPO), high molecular agent B (styrene-grafted ethene-GMA multipolymer) 25 modulation polyester modification agent B.
Respectively with regard to above-mentioned modifier A and properties-correcting agent B, add 5 quality %, 10 quality %, 15 quality % in the regenerative PET that in embodiment 2, uses, find out the relation of shearing rate and melt viscosity.It the results are shown in Figure 2 and Fig. 3.
As shown in Figures 2 and 3, add modifier A and properties-correcting agent B5 quality %, the phenomenon that hangs just is prevented from, and abnormity is shaped and also becomes possibility, and the formedness of injection molded also can be predicted.
Also have, aspect the regenerative PET that has added modifier A and properties-correcting agent B, under the condition of 260～280 ℃ of scopes of forming temperature, carry out injection molded in the mould that has the spirrillum chamber, determine the helical length in the die cavity, it the results are shown in Figure 4 and Fig. 5.
According to Fig. 4 and Fig. 5, add modifier A and properties-correcting agent B5 weight %, the situation that helical length and nothing are added is more than on an equal basis, also according to modifier A and properties-correcting agent B, show the good flowability of each sample melts in mould, injection molded is not only hindered, and is modified on the contrary.
Embodiment 4
Mainly use following tackifier as tackifier; tackifier A (new LDPE (film grade) (LDPE): MFR 4.0g/10 branch); tackifier B (reactivity-TPO, MFR 0.6g/10 branch); mainly use following high molecular agent as the high molecular agent; high molecular agent A (SBS that contains epoxy group(ing)); high molecular agent B (styrene-grafted ethene-GMA multipolymer EGMA-g-PS) SBS; above-mentioned tackifier and above-mentioned high molecular agent prescription, after the mixing back of combination roller, pulverizing, granulating, modulate polyester resin modifier according to table 4 and table 5.
The waste product crushed material (regenerative PET) of above-mentioned each properties-correcting agent and PET bottle according to the prescription shown in table 4 and the table 5, is carried out that dry type is mixed, fusion is mixed in extrusion shaper then, extrudes ribbon from nozzle at last, in water, cut off again, make apparent granulation with cutting knife.Just not dry each particulate material of filling a prescription, also to measure machine (trade(brand)name Capillo graph) with regard to the melt viscosity that each particle sample uses Japan smart machine company to make, at mouth die orifice footpath 1mm, measure 270 ℃ of temperature, measure melt viscosity under the condition of 300 seconds warm up time.It the results are shown in Table 4 and table 5
210～256 ℃ of barrel temperatures, screw rod; Φ 30,2 of reverse directions, full helical (fullflight), L/D=2.5, venting hole (open vent), 100rpm, mouthful mould; 3.5 * 15mm, tape formula mouth mould (ribbon dye), extrusion molding under the condition of buffer layer (breaker strip) is arranged, observe the phenomenon of confirming to hang (the shape volt retentivity of the resin that comes out from the mouth mould according to naked eyes, the situation that hangs that occurs because of deadweight), it the results are shown in Table 4 and table table 5.
Table 4
| Sample No. (embodiment 4) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
| Regenerative PET (mass parts) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Tackifier (mass parts) | A(LDPE) | 3 | 10 | 3 | 15 | 20 | 100 | 100 | |
| B (reactive TPO) | 3 | ||||||||
| A (SBS that contains epoxy group(ing)) | 1 | 1 | 3 | 5 | 20 | 10 | 20 | ||
| B(PS-g-EGMA) | 1 | ||||||||
| Tackifier: high molecule ratio agent (recipe ratio) | 3∶1 | 10∶1 | 1∶1 | 3∶1 | 1∶1 | 10∶1 | 5∶1 | 3∶1 | |
| Melt viscosity (pool) | 6.08×10 1sec -1*5 | 640 | 960 | 700 | 2170 | 3410 | 3010 | 4120 | 660 |
| 1.22×10 2sec -1*5 | 720 | 850 | 710 | 1370 | 2280 | 2280 | 2830 | 720 | |
| 2.43×10 2sec -1*5 | 620 | 720 | 580 | 840 | 1670 | 1560 | 2020 | 540 | |
| Extrude situation *5 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
*5: shearing rate
*6: *: the phenomenon that hangs significantly, zero is arranged: the phenomenon that hangs is improved
Table 5
| Sample No. (embodiment 4) | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | |
| Regenerative PET (mass parts) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Tackifier (mass parts) | A(LDPE) | 15 | 13 | ||||||
| B (reactive TPO) | 15 | 100 | 15 | 7 | |||||
| D(SEBS) | 15 | 15 | 1 | 7 | |||||
| High molecular agent (mass parts) | A (SBS that contains epoxy group(ing)) | 5 | 5 | 4 | |||||
| B(PS-g-EGMA) | 5 | 20 | 5 | 5 | 4 | ||||
| Tackifier: high molecule ratio agent (recipe ratio) | 3∶1 | 5∶1 | 3∶1 | 3∶1 | 3∶1 | 3∶1 | 7∶2 | 7∶2 | |
| Melt viscosity (pool) | 6.08×10 1sec -1*7 | 3110 | 8800 | 3880 | 4710 | 1730 | 3470 | 2250 | 3920 |
| 1.22×10 2sec -1*7 | 2470 | 6100 | 3140 | 3740 | 1460 | 2650 | 1830 | 3220 | |
| 2.43×10 2sec -1*7 | 1210 | 4100 | 2530 | 2840 | 1250 | 1920 | 1410 | 2690 | |
| Extrude situation *8 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
*7: shearing rate
*8: *: the phenomenon that hangs significantly, zero is arranged: the phenomenon that hangs is improved
[comparative example)
As the comparative example of the foregoing description, according to the prescription shown in the table 6, and the method mensuration melt viscosity same with the foregoing description, confirm the phenomenon that hangs in extrusion molding, whether to occur.It the results are shown in Table 6.
Table 6
| Sample No. (comparative example) | 1 | 2 | 3 | 4 | 5 | 6 | |
| Regenerative PET (mass parts) | 100 | 100 | 100 | 100 | 100 | 100 | |
| Tackifier (mass parts) | A(LDPE) | 1 | 0.5 | 120 | 300 | ||
| High molecular agent (mass parts) | A (SBS that contains epoxy group(ing)) | 1 | 1 | 20 | 20 | ||
| Tackifier: high molecular agent (recipe ratio) | 1∶1 | 1∶2 | 6∶1 | 15∶1 | |||
| Melt viscosity (pool) | 6.08×10 1sec -1*9 | 1160 | 490 | 420 | 530 | 4980 | 4050 |
| 1.22×10 2sec -1*9 | 1380 | 200 | 540 | 460 | 3270 | 3080 | |
| 2.43×10 2sec -1*9 | 1310 | 60 | 500 | 340 | 2360 | 2350 | |
| Extrude situation *10 | ○ | × | × | × | ○ | ○ | |
| Predrying (150 ℃, 4 hours) | Have | Do not have | Do not have | Do not have | Do not have | Do not have | |
*9: shearing rate
*10: *: the phenomenon that hangs significantly, zero is arranged: the phenomenon that hangs is improved
The sample No.1 of the comparative example shown in the table 6 has been to use in the thermostat container of 150 ℃ of temperature by predrying 4 hours regenerative PET.
With reference to the result shown in table 4 and the table 5, by pre-dried embodiment (sample No.1～sample No.16), wherein the resin combination of any prescription, the phenomenon that hangs all are not prevented from.
As for the sample N0.2 of the comparative example that does not add tackifier shown in the table 6 and high molecular agent, the sample No.3 that tackifier are discontented with the comparative example of 3 mass parts, and discontented 3 mass parts of tackifier, the high molecular agent is at the sample No.4 of the comparative example of the following addition of equivalent, because of all not obtaining necessary melt viscosity through predrying for extrusion molding etc., and the serious phenomenon that hangs appears.
Under the situation of regenerative PET 100 mass parts being added the above tackifier of 100 mass parts, (in comparative example sample No.5, be 120 mass parts, in comparative example sample No.6, be 300 mass parts), for extrusion molding etc. sufficient melt viscosity has been arranged, as long as resin combination of the present invention has had necessary melt viscosity at extrusion molding etc., necessity that regenerative PET (vibrin) 100 mass parts are not added most tackifier, the tackifier that added volume on the contrary can make the intermiscibility of tackifier and vibrin worsen on the contrary, the infringement molding (such as, with the molding of comparative example sample No.6 formed thereby) problem of cosmetic look will take place, so do not wish too much to add tackifier.
From the shaping thing of the resin combination formed thereby shown in the foregoing description, the aesthetic property of its outward appearance is good, and should sufficient shock-resistance have been arranged the shaping thing.Even should the shaping thing be that the foaming and molding thing is also passable.
The melt viscosity of vibrin is according to the interpolation of above-mentioned tackifier and modified, particularly to do the lower molecular weight change the recycled polyester resin add the high molecular agent again, its melt viscosity is just increased significantly, the phenomenon that hangs of shaping thing that hangs when phenomenon and extrusion molding of the vibrin that comes out from nozzle when injection molded is just sent out and is prevented from, not only injection molded is kept well, and shock-resistance is also modified.
When the also useful polyester and resin composition that contains tackifier and high molecular agent carries out injection molded or extrusion molding.With regard to unnecessary vibrin is carried out predrying or attract dewatering, that is to say that pre-dried cost of equipment of the expense of needn't deflorating and design have the cost of equipment of the special extrusion shaper of venting hole, and saved dewatered time and trouble.
Thereby only limit in the past laminar, fibrous, the container-like vibrin shaping thing different shape that can be shaped now, the vibrin that particularly is used in the polyester and resin composition of the present invention is regenerating resins such as exhausted PET bottle, so the regeneration rate just improves relatively.
Claims (3)
1, a kind of polyester resin modifier, its contain melt flow rate (MFR) be 20g/10 divide following tackifier and have can with the functional group's of vibrin reaction high molecular agent.
2, polyester resin modifier as claimed in claim 1, wherein, described tackifier are polypropylene and elastomeric polymer alloy.
3, polyester resin modifier as claimed in claim 1 or 2, wherein, described tackifier mix mutually with the mass ratio of described high molecular agent with 6: 4～9: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02119941 CN1458187A (en) | 2002-05-13 | 2002-05-13 | Polyester resin composition, polyester resin modifier and resin formed article |
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| CN 02119941 Division CN1458187A (en) | 2002-05-13 | 2002-05-13 | Polyester resin composition, polyester resin modifier and resin formed article |
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| CN1955220A true CN1955220A (en) | 2007-05-02 |
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| CN 02119941 Pending CN1458187A (en) | 2002-05-13 | 2002-05-13 | Polyester resin composition, polyester resin modifier and resin formed article |
| CN 200610006240 Pending CN1955220A (en) | 2002-05-13 | 2002-05-13 | Polyester resin composite and polyester resin medifier and resin molding |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747601B (en) * | 2008-12-11 | 2014-04-02 | 第一毛织株式会社 | Environmentally friendly thermoplastic resin composition using recycled polyester resin |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120868B (en) * | 2011-04-08 | 2012-07-04 | 扬州三星塑胶有限公司 | Toughening process for high-tensile-strength recycled polyester sheet |
| CN103741326B (en) * | 2013-12-17 | 2015-03-25 | 葛小飞 | Method for preparing wear-proof cotton and linen fabric |
| CN110042516A (en) * | 2019-03-14 | 2019-07-23 | 宁波三邦超细纤维有限公司 | Coloured Chinese fiber crops composite antibacterial superfine fibre and preparation method thereof |
| CN109943903A (en) * | 2019-03-14 | 2019-06-28 | 宁波三邦超细纤维有限公司 | Regenerative environment-friendly superfine fibre and preparation method thereof |
| CN110004516A (en) * | 2019-03-14 | 2019-07-12 | 宁波三邦超细纤维有限公司 | Regenerative environment-friendly antibacterial functions fiber and preparation method thereof |
| CN110004517A (en) * | 2019-03-14 | 2019-07-12 | 宁波三邦超细纤维有限公司 | Original liquid coloring regenerative environment-friendly functional fibre and preparation method thereof |
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2002
- 2002-05-13 CN CN 02119941 patent/CN1458187A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747601B (en) * | 2008-12-11 | 2014-04-02 | 第一毛织株式会社 | Environmentally friendly thermoplastic resin composition using recycled polyester resin |
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