CN104926972A - Amorphous alpha-olefin copolymer and application thereof in preparation of non-woven fabric hot melt adhesive - Google Patents
Amorphous alpha-olefin copolymer and application thereof in preparation of non-woven fabric hot melt adhesive Download PDFInfo
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- CN104926972A CN104926972A CN201510316861.5A CN201510316861A CN104926972A CN 104926972 A CN104926972 A CN 104926972A CN 201510316861 A CN201510316861 A CN 201510316861A CN 104926972 A CN104926972 A CN 104926972A
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- olefin copolymer
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Abstract
The invention discloses an amorphous alpha-olefin copolymer formed by copolymerizing ethylene, propylene and 1-butylene. The amorphous alpha-olefin copolymer comprises the following raw materials: 10 to 15 percent of ethylene, 55 to 60 percent of propylene and 25 to 30 percent of 1-butylenes, and is prepared according to a preparation method comprising the following steps: using straight chain saturated alkane as a solvent, adding a main catalysis and a promoter; pumping in hydrogen; carrying out copolymerization at 0.6 to 2.0 MPa and 60 to 100 DEG C for 2 to 3 hours; carrying out distillation to separate out the solvent, so as to obtain the product amorphous alpha-olefin copolymer. The amorphous alpha-olefin copolymer provided by the invention has the advantages of being low in processing temperature and energy consumption, high in cohesiveness, excellent in heat resistance, ageing resistance, ultraviolet resistance, water resistance and weatherability, environment-friendly, pollution-free, proper in opening time, and the like, when being used for preparation of an hot melt adhesive used in the non-woven fabric hot melting spray-bonding process, and not only is suitable for automatic mass production, but also can meet the requirements of small-scale production.
Description
Technical field
The present invention relates to a kind of non-crystalline state ɑ-olefin copolymer, and preparation method thereof, and it is preparing the application in non-woven fabrics hot melt adhesive.
Background technology
Hot melt adhesive (English name: Hot Glue) is a kind of plastic tackiness agent, and in certain temperature range, its physical condition changes with temperature change, and chemical property is constant, and it is nonpoisonous and tasteless, belongs to environmental-protecting chemical product.Hot melt adhesive is with solid-state existence under envrionment temperature, is undertaken spraying, bonding by heating and melting, and final cooling curing realizes bonding effect.Compared with other tackiness agent, the most important advantage of hot melt adhesive is do not have solvent, desolventizes process after avoiding applying glue to terminate, and no matter this is the work condition environment to Process of Applying Glue, or all has better environment-friendly advantage to the product of bonding in following use procedure.Non-woven fabrics hot melt spray-bonding craft adopts the hot melt adhesive of particular requirement to carry out bonding technique to the product taking non-woven fabrics as base material, be mainly used in disposable sanitary articles, specifically comprise baby's disposable urine trousers, hospital pads, feminien hygiene cotton, adult incontinence briefs and surgical drapes etc.The non-woven fabrics hot melt adhesive being applied to disposable sanitary articles generally adopts spray-bonding craft, instead of traditional coating process, can greatly reduce hot melt adhesive usage quantity like this, and in spray-bonding craft, tradition adopts spiral glue spraying mode, and up-to-date glue spraying mode is fiber glue spraying, the latter more can save glue consumption than the former.Glue spraying temperature is very important to hot melt spray-bonding craft, and alap glue spraying temperature is conducive to the energy and environmental requirement.This just requires that polymkeric substance has lower softening temperature, and have good hot melt mobility, dispersiveness is beneficial to glue spraying; The force of cohesion that can not reduce again polymkeric substance itself has good bonding strength after ensureing cooling curing.These all require that the polymkeric substance in hot melt adhesive puts in order at component, molecular weight distribution, inner monomer, meet specific condition in orientation etc.Time simultaneously in order to ensure that downstream client uses hot melt adhesive, can not block glue-spraying machine because colloid is aging, polymkeric substance also must by 72 hours aging tests at 180 DEG C.
That produces APAO at present in the world has four enterprises, and be that Germany wins wound (EVONIK) group respectively, REXtac company of the U.S., U.S. Yi Shiman (EASTMAN) chemical company, China very reaches chemical industry.Second third fourth terpolymer polymkeric substance involved by the application only has German Ying Chuan group to produce, and the APAO that the said firm is applied to non-woven fabrics glue spraying field exists certain defect in actual applications, can not be advantageously applied to fiber spray-bonding craft.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of non-crystalline state ɑ-olefin copolymer (English Amorphous Poly Alpha-Olefin by ethene, propylene and 1-butylene copolymerization, abbreviation APAO), and preparation method thereof, and it is preparing the application in non-woven fabrics hot melt adhesive.
The present invention is achieved by the following technical solutions:
By non-crystalline state ɑ-olefin copolymer of ethene, propylene and 1-butylene copolymerization, be with ethene, propylene and 1-butylene for raw material is prepared from, wherein, ethene accounts for 10 ~ 15% of total raw material consumption; Propylene accounts for 55 ~ 60% of total raw material consumption; 1-butylene accounts for 25 ~ 30% of total raw material consumption, and its preparation method is as follows:
With straight chain saturated alkane for solvent, add feed ethylene, propylene and 1-butylene, add Primary Catalysts and promotor, pass into hydrogen (as molecular weight regulator), copolyreaction is carried out under pressure 0.6 ~ 2.0MPa, temperature 60 ~ 100 DEG C (preferably 80 ~ 90 DEG C) condition, react 2 ~ 3 hours, steam solvent, products therefrom is non-crystalline state ɑ-olefin copolymer.
Described straight chain saturated alkane is C
6~ C
10straight chain saturation alkane, preferred normal hexane, normal heptane.
The consumption of described straight chain saturation alkane is 1 ~ 1.5 times of raw material gross weight.
Described Primary Catalysts is the effective catalyst (Authorization Notice No. is the catalyzer recorded in the Chinese invention patent of CN101942053 B, catalyzer prepared by preferred embodiment 1,2,3) for the preparation of the random alpha olefin copolymer of height.
Described promotor is triethyl aluminum.
The consumption of described Primary Catalysts, promotor is respectively 0.0005% of raw material gross weight, 0.0025%.
The consumption of described hydrogen is 0.001 ~ 0.01% of raw material gross weight.
The temperature of described distillation controls at 70 ~ 140 DEG C, and pressure is 0.05 ~ 0.2MPa.
Non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization of the present invention, may be used for preparing non-woven fabrics hot melt adhesive, preparation method is: get the non-crystalline state ɑ-olefin polymer of 50 ~ 60%, the softening agent (mineral oil) of 9 ~ 12%, the tackifier (hydrogenating carbon 5 resin) of 30 ~ 40% and 1 ~ 2% oxidation inhibitor, each raw material percentage, mixing mixing, adding hot preparation hot melt adhesive, being applied to non-woven fabric spray adhesive process by preparing gained hot melt adhesive.The raw material of the routine of hot melt adhesive prepared by softening agent used, oxidation inhibitor, tackifier etc. for this area.
Non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization of the present invention, number-average molecular weight 3000 ~ 7000, preferably 4500 ~ 5500; Molecular weight distribution 5 ~ 8, preferably 6 ~ 7; Melt viscosity (cloth is as a gram Field rotary viscometer method) when 190 DEG C is 2000 ~ 8000cp, preferably 2500 ~ 4000cp; Ring and ball softening point (GB/T4507-1999) is at 120 ~ 125 DEG C; Penetration degree (GB/T4509-2010) is at 60 ~ 75dmm (100g/25 DEG C/5s).During by the hot melt adhesive of this multipolymer for the preparation of non-woven fabrics hot melt spray-bonding craft, there is processing temperature low, energy consumption is low, cohesiveness is strong, good heat-proof aging, ultraviolet resistance, water-fast, weathering resistance, and environment friendly and pollution-free, the advantages such as the open hour are suitable, both adapted to automatic mass production, and can small-scale production be met again.
Accompanying drawing explanation
Fig. 1: embodiment 1 gained tree lace photo.
Fig. 2: embodiment 2 gained tree lace photo.
Fig. 3: embodiment 3 gained tree lace photo.
Fig. 4: embodiment 4 gained tree lace photo.
Fig. 5: embodiment 5 gained tree lace photo.
Fig. 6: the photo of embodiment 3 gained glue spraying.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Instrument, reagent, material etc. involved in following embodiment, unless otherwise noted, be existing conventional instrument, reagent, material etc. in prior art, obtain by regular commercial sources.Experimental technique involved in following embodiment, detection method etc., unless otherwise noted, are existing normal experiment method in prior art, detection method etc.
Embodiment 1 prepares the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization
Feed ethylene, propylene and 1-butylene with magnitude relation in table 1, preparation method is as follows:
Take normal heptane as solvent, add feed ethylene, propylene and 1-butylene, add Primary Catalysts and promotor, pass into hydrogen (as molecular weight regulator), copolyreaction is carried out under pressure 1.2MPa, temperature 80 ~ 90 DEG C of (see table 1) conditions, react 2 hours, steam solvent, products therefrom is non-crystalline state ɑ-olefin copolymer.
The consumption of described normal heptane is 1 times of raw material gross weight.
Described Primary Catalysts is Authorization Notice No. is the catalyzer that in the Chinese invention patent of CN 101942053 B, embodiment 1 is recorded.
Described promotor is triethyl aluminum.
The consumption of described Primary Catalysts and promotor is respectively 0.0005% of raw material gross weight, 0.0025%.
The consumption of described hydrogen is 0.008% of raw material gross weight.
The temperature of described distillation controls at 80 ~ 130 DEG C, and pressure is 0.05MPa.
The molecular weight, melt viscosity, softening temperature, penetration degree etc. of gained non-crystalline state ɑ-olefin copolymer are in table 1.
Embodiment 2 prepares the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization
Feed ethylene, propylene and 1-butylene with magnitude relation in table 1, the other the same as in Example 1.
Embodiment 3 prepares the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization
Feed ethylene, propylene and 1-butylene with magnitude relation in table 1, the other the same as in Example 1.
Embodiment 4 prepares the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization
Feed ethylene, propylene and 1-butylene with magnitude relation in table 1, the other the same as in Example 1.
Embodiment 5 prepares the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization
Feed ethylene, propylene and 1-butylene with magnitude relation in table 1, the other the same as in Example 1.
Embodiment 6 prepares the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization
The consumption of feed ethylene, propylene and 1-butylene is respectively: 12%, 58%, 30%, the other the same as in Example 1.
Table 1
With the multipolymer of above-described embodiment 1 ~ 5 preparation for hot melt adhesive prepared by raw material, preparation method is: get the non-crystalline state ɑ-olefin polymer of 55%, the softening agent (mineral oil) of 10%, the tackifier (hydrogenating carbon 5 resin) of 34% and 1% oxidation inhibitor, each raw material percentage, mixing mixing, add hot preparation hot melt adhesive, fiber spray-bonding craft is adopted to obtain tree lace at 160 DEG C, as shown in Fig. 1 ~ Fig. 5, as seen from the figure, embodiment 3 ~ 5 all embodies good fiber glue spraying performance; And all embodiments all embody good glue spraying performance (as shown in Figure 6) in conventional helical spray-bonding craft.
In addition, the multipolymer prepared with embodiment 6, (its ethylene content is 25% to win with Germany the APAO creating (EVONIK) group and produce; Propylene content is 60%; Butene content is 15%), contrast, result is as shown in table 2, table 3.
Table 2
Table 3
Conclusion: found by contrast, first in apparent index, the other side's product is in viscosity, and namely molecular weight is relatively, but in softening temperature and penetration degree, difference is very large; Next is interior in physical property, and product of the present invention has lower degree of crystallinity.
Claims (9)
1., by non-crystalline state ɑ-olefin copolymer of ethene, propylene and 1-butylene copolymerization, it is characterized in that: be with ethene, propylene and 1-butylene for raw material is prepared from, wherein, ethene accounts for 10 ~ 15% of total raw material consumption; Propylene accounts for 55 ~ 60% of total raw material consumption; 1-butylene accounts for 25 ~ 30% of total raw material consumption, and its preparation method is as follows:
With straight chain saturated alkane for solvent, add feed ethylene, propylene and 1-butylene, add Primary Catalysts and promotor, pass into hydrogen (as molecular weight regulator), copolyreaction is carried out under pressure 0.6 ~ 2.0MPa, temperature 60 ~ 100 DEG C of conditions, react 2 ~ 3 hours, steam solvent, products therefrom is non-crystalline state ɑ-olefin copolymer;
Described straight chain saturated alkane is C
6~ C
10straight chain saturation alkane;
The consumption of described straight chain saturation alkane is 1 ~ 1.5 times of raw material gross weight;
Described Primary Catalysts is the effective catalyst for the preparation of the random alpha olefin copolymer of height;
Described promotor is triethyl aluminum.
2. the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization according to claim 1, is characterized in that: described straight chain saturated alkane is selected from normal hexane, normal heptane.
3. the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization according to claim 1, is characterized in that: the consumption of described Primary Catalysts, promotor is respectively 0.0005% of raw material gross weight, 0.0025%.
4. the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization according to claim 1, is characterized in that: the consumption of described hydrogen is 0.001 ~ 0.01% of raw material gross weight.
5. the non-crystalline state ɑ-olefin copolymer by ethene, propylene and 1-butylene copolymerization according to claim 1, is characterized in that: the temperature of described distillation controls at 70 ~ 140 DEG C, and pressure is 0.05 ~ 0.2MPa.
6. according to any one of Claims 1 to 5 by the preparation method of the non-crystalline state ɑ-olefin copolymer of ethene, propylene and 1-butylene copolymerization, it is characterized in that: with straight chain saturated alkane for solvent, add feed ethylene, propylene and 1-butylene, add Primary Catalysts and promotor, pass into hydrogen (as molecular weight regulator), copolyreaction is carried out under pressure 0.6 ~ 2.0MPa, temperature 60 ~ 100 DEG C of conditions, react 2 ~ 3 hours, steam solvent, products therefrom is non-crystalline state ɑ-olefin copolymer.
7. according to any one of Claims 1 to 5, preparing the application in hot melt adhesive by the non-crystalline state ɑ-olefin copolymer of ethene, propylene and 1-butylene copolymerization.
8. application according to claim 7, it is characterized in that: application method is: get the non-crystalline state ɑ-olefin polymer of 50 ~ 60%, the softening agent of 9 ~ 12%, the tackifier of 30 ~ 40% and 1 ~ 2% oxidation inhibitor, each raw material percentage, mixing mixing, adding hot preparation hot melt adhesive, being applied to non-woven fabric spray adhesive process by preparing gained hot melt adhesive.
9. a hot melt adhesive, it is characterized in that: prepare by the following method: get the non-crystalline state ɑ-olefin polymer of 50 ~ 60%, the softening agent of 9 ~ 12%, the tackifier of 30 ~ 40% and 1 ~ 2% oxidation inhibitor, each raw material percentage, mixing mixing, heating is prepared into hot melt adhesive.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109161034A (en) * | 2018-08-20 | 2019-01-08 | 辽阳辽化奇达化工有限责任公司 | A kind of emulsification method of amorphous state alpha olefin copolymer |
| CN110951418A (en) * | 2018-09-26 | 2020-04-03 | 东莞市台煜塑胶科技有限公司 | Carbon cloth composite hot melt adhesive and preparation method thereof |
| CN112654650A (en) * | 2018-09-06 | 2021-04-13 | 赢创运营有限公司 | Amorphous polyalphaolefins and their use in hot melt compositions with improved sprayability |
| CN113968941A (en) * | 2021-12-06 | 2022-01-25 | 方昱炜 | Polymerization method of acrylic modified poly-alpha-olefin |
| CN114605580A (en) * | 2022-01-26 | 2022-06-10 | 方昱炜 | Synthesis of polyolefin rubber regenerant |
| CN114958256A (en) * | 2022-06-14 | 2022-08-30 | 上海长园电子材料有限公司 | High-adhesion APAO hot melt adhesive and preparation method thereof |
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| CN103124777A (en) * | 2010-09-27 | 2013-05-29 | 汉高股份有限及两合公司 | Bonding using hot-melt adhesives |
| CN103194159A (en) * | 2013-04-17 | 2013-07-10 | 岳阳东方雨虹防水技术有限责任公司 | Hot-melt pressure-sensitive adhesive and preparation method thereof |
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| WO2002034856A1 (en) * | 2000-10-27 | 2002-05-02 | Seong Il Chemical Co., Ltd. | Hot-melt adhesive for electronic components |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161034A (en) * | 2018-08-20 | 2019-01-08 | 辽阳辽化奇达化工有限责任公司 | A kind of emulsification method of amorphous state alpha olefin copolymer |
| CN112654650A (en) * | 2018-09-06 | 2021-04-13 | 赢创运营有限公司 | Amorphous polyalphaolefins and their use in hot melt compositions with improved sprayability |
| CN110951418A (en) * | 2018-09-26 | 2020-04-03 | 东莞市台煜塑胶科技有限公司 | Carbon cloth composite hot melt adhesive and preparation method thereof |
| CN113968941A (en) * | 2021-12-06 | 2022-01-25 | 方昱炜 | Polymerization method of acrylic modified poly-alpha-olefin |
| CN113968941B (en) * | 2021-12-06 | 2023-09-08 | 方昱炜 | Polymerization method of acrylic modified poly alpha olefin |
| CN114605580A (en) * | 2022-01-26 | 2022-06-10 | 方昱炜 | Synthesis of polyolefin rubber regenerant |
| CN114958256A (en) * | 2022-06-14 | 2022-08-30 | 上海长园电子材料有限公司 | High-adhesion APAO hot melt adhesive and preparation method thereof |
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