CN103641955A - Polyolefin ionomer and application thereof - Google Patents
Polyolefin ionomer and application thereof Download PDFInfo
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- CN103641955A CN103641955A CN201310604509.2A CN201310604509A CN103641955A CN 103641955 A CN103641955 A CN 103641955A CN 201310604509 A CN201310604509 A CN 201310604509A CN 103641955 A CN103641955 A CN 103641955A
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Abstract
The invention discloses a polyolefin ionomer and application thereof. The polyolefin ionomer is characterized in that: uniformly mixing an alcohol ketone acid, lanthanum maleate and water to prepare a paste, then uniformly mixing the paste, an initiator and polyolefin, and performing a fusion grafting reaction at a certain temperature, wherein the alcohol ketone acid can be pyruvic acid, glycollic acid, citric acid, malic acid or a mixed alcohol ketone acid prepared from the above two or three alcohol ketone acids with a random ration. The polyolefin ionomer provided by the invention can be used as a compatilizer for improving the blending compatitility of polycaprolactam and polyethylene, and can be used to prepare a polycaprolactam/polyolefin ionomer/polyethylene ternary alloy system.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation and application thereof of polyolefin ionomers.
Background technology
Organic polymer material is as one of current three large materials, has abundant raw material, cost is low, quality is light and the advantage such as easy machine-shaping, in the development of productive life field rapidly.But what at present realized scale operation is mostly commodity polymer material, they exist the shortcomings such as poor mechanical property, thermotolerance are low, these drawbacks limit the application of macromolecular material.In order to make up above-mentioned defect, the alloying of macromolecular material and high performance are its developing direction.
Ionomer refers to the polymkeric substance that contains a small amount of ionic group on macromolecular chain, is also referred to as from aggressiveness, and wherein the content of ionic group is no more than 15%.In polymkeric substance, introduce after ionic group intramolecule can produce the unexistent special role of general polymer system: ion---ionic interaction, ion---dipolar interaction and interaction of hydrogen bond etc.These special interactions make ionomer have important application at polymeric material field.In polymer modification, ionomer is commonly used for stablizer, crystallization nucleating agent and compatilizer etc., is a kind of good functional agent.
At present, preparing the more ripe method of ionomer, to mainly contain copolymerization process and Graft Method copolymerization process be the ionomeric predominant methods of preparation, its basic ideas are first monomer copolymerization to be become to the multipolymer with polar group, and then polar copolymer is neutralized into ionomer copolymerization process can obtains compared with the ionomer of high ionization degree with alkali or acid, but severe reaction conditions, is difficult to realize industrialization.Graft Method is can be by the method for the direct functionalization of polymer molecule, and its thinking roughly has two: (1) is grafting polar group on macromolecular chain first, and the method for then using saponification reaction is by polymkeric substance and salify; (2) first synthesize the metal complexes monomer containing unsaturated link(age), and then to polymer, make ionomer by monomer-grafted.For copolymerization process, Graft Method reaction conditions is comparatively gentle, is easy to realize scale operation, and Graft Method is very applicable for only needing the situation of low degree of ionization.
Summary of the invention
The object of the present invention is to provide a kind of polyolefin ionomers and its preparation method and application, it is characterized in that improving the dispersiveness of metal complexes monomer in polyolefine by introducing alcohol ketone acid, and improve the percentage of grafting of graft reaction.The present invention provides new reference for preparing high-performance polyolefin ionomers.
For realizing the technical scheme that the object of the invention adopts, be: a kind of polyolefin ionomers of the present invention, is made 1 by following method) first alcohol ketone acid, maleic acid lanthanum and water are uniformly mixed into paste; 2) paste, initiator and polyolefine are mixed again, and under certain temperature, implement melting graft reaction and make polyolefin ionomers, described alcohol ketone acid has a kind of pyruvic acid, oxyacetic acid, citric acid, oxysuccinic acid of being selected from least.
(1) take weight part formula as
A, paste formula are:
Maleic acid lanthanum 100
Alcohol ketone acid 5-25
Water 50-200
The reactant formula of b, polyolefin ionomers is:
Polyolefine 100
Initiator 0.3-1
Paste 1-10;
(2) preparation process is:
Toward processing units, drop into maleic acid lanthanum, alcohol ketone acid and water, at 15-40 ℃, mix, obtain paste; Toward processing units, drop into polyolefine and initiator again, secondary mixes, and at 165-195 ℃ melting graft reaction 5-20 minute, discharging, cooling, obtains polyolefin ionomers.
Described polyolefine has a kind of polyethylene, polypropylene or polyethylene propylene multipolymer of being selected from least.The plural arbitrary proportion that can be polyethylene, polypropylene or polyethylene propylene multipolymer mixes.
Described initiator is benzoyl peroxide (BPO), dicumyl peroxide (DCP) or azo-bis-isobutyl cyanide (AIBN).
For realizing the technical scheme that the object of the invention adopts, be: the preparation method of a kind of polyolefin ionomers of the present invention, comprise the steps: first alcohol ketone acid, maleic acid lanthanum and water to be uniformly mixed into paste, again paste, initiator and polyolefine are mixed, and implement melting graft reaction under certain temperature, it is characterized in that:
(1) take weight part formula as
A, paste
Maleic acid lanthanum 100
Alcohol ketone acid 5-25
Water 50-200
B, polyolefin ionomers
Polyolefine 100
Initiator 0.3-1
Paste 1-10;
(2) preparation process is:
Toward processing units, drop into maleic acid lanthanum, alcohol ketone acid and water, at 15-40 ℃, mix, obtain paste; Toward processing units, drop into polyolefine and initiator again, secondary mixes, and at 165-195 ℃ melting graft reaction 5-20 minute, discharging, cooling, obtains polyolefin ionomers.
Alcohol ketone acid of the present invention refers to pyruvic acid, oxyacetic acid, citric acid, oxysuccinic acid, or the alcohol mixture ketone acid that mixes of the arbitrary proportion of above-mentioned two or three alcohol ketone acid.
Polyolefine of the present invention refers to polyethylene, polypropylene or polyethylene propylene multipolymer, or the mixing polyolefine that mixes of above-mentioned two or three polyolefinic arbitrary proportion.
The present invention is to initiator indefinite, as long as can cause the reagent of free radical, can select conventional peroxide and azo-initiator, as benzoyl peroxide (BPO), dicumyl peroxide (DCP) and azo-bis-isobutyl cyanide (AIBN) etc.The preferred DCP of the present invention makes initiator.
Another object of the present invention is to provide the preparation method of polycaprolactam/polyolefin ionomers/polyethylene alloy, it is characterized in that, obtains as follows:
By 100 weight part polycaprolactams, 15-25 weight account polyethylene, the polyolefin ionomers that the above-mentioned preparation method of 1-6 weight part makes, 0.3-0.6 weight part oxidation inhibitor mixes at 20-80 ℃, obtains mixture; Mixture being placed at 230-250 ℃ of temperature to melting closes and mixes again.Described oxidation inhibitor refers to antioxidant 1010, antioxidant 1076 or irgasfos 168, or the mixing oxidation inhibitor that mixes of the arbitrary proportion of above-mentioned two kinds of oxidation inhibitor, the mixing oxidation inhibitor preferably being mixed by antioxidant 1010 and the irgasfos 168 of 1:1 weight ratio.
Advantage of the present invention is: 1. the present invention prepares ionomer by original position melt grafting, and technique is simple, easily realizes industrialization; 2. introduce alcohol ketone acid and water, increased the dispersed homogeneous degree in polyolefine of maleic acid lanthanum, improve percentage of grafting, thereby overcome the problems such as the inhomogeneous and percentage of grafting of traditional dispersion directly maleic acid lanthanum and polyolefine melt blending being brought is low.3. the polyolefin ionomers of gained of the present invention can be used as the expanding material of polycaprolactam/polyethylene (PA6/PE) blend alloy.
Accompanying drawing explanation
Fig. 1 is infrared spectrogram, and in Fig. 1, A1, B1, C1, D1 curve are respectively maleic acid lanthanum, pure PE(comparative example 1), the infrared spectrum of comparative example 3 and embodiment 2 samples.
Fig. 2 is infrared spectrogram, and in Fig. 2, A2, B2, C2 are respectively maleic acid lanthanum, pure PP(comparative example 2) and the infrared spectrum of embodiment 3 samples.
Fig. 3, Fig. 4 are dynamic rheological property graphic representation.Wherein, A1 and A2 are respectively storage modulus (G') and out-of-phase modulus (G'') curve of polycaprolactam/polyethylene alloy sample in comparative example 4; B1 and B2 are respectively G' and the G'' curve of polycaprolactam/polypropylene ionomer/polyethylene alloy sample of embodiment 7; C1 and C2 are respectively G' and the G'' curve of polycaprolactam/polyethylene ionomer/polyethylene alloy sample of embodiment 8.
Embodiment
By specific embodiment, the present invention is done to statement more in detail below, rather than limit the invention.
One, the preparation of polyolefin ionomers
In Banbury mixer, first drop into 100g maleic acid lanthanum, 5g pyruvic acid and 50g water, at 15 ℃, mix, obtain paste; Drop into 10 kilograms of (10000g) polyethylene and 30g benzoyl peroxide (BPO), secondary mixes again, and is warming up at 165 ℃ melting graft reaction 20 minutes, and discharging, cooling, obtains polyethylene ionomer.Through recording maleic acid lanthanum and poly percentage of grafting, be that the apparent morphology observation of 0.24%, SEM is not found agglomerating particles.
Embodiment 2
In Banbury mixer, first drop into 200g maleic acid lanthanum, 20g oxyacetic acid and 200g water, at 35 ℃, mix, obtain paste; Drop into 10 kilograms of (10000g) polyethylene and 50g dicumyl peroxide (DCP), secondary mixes again, and is warming up at 180 ℃ melting graft reaction 12 minutes, and discharging, cooling, obtains polyethylene ionomer.Through recording maleic acid lanthanum and poly percentage of grafting, be 0.56%.The apparent morphology observation of SEM is not found agglomerating particles.
Embodiment 3
In Banbury mixer, first drop into 300g maleic acid lanthanum, 45g oxysuccinic acid and 400g water, at 25 ℃, mix, obtain paste; Drop into 10 kilograms of (10000g) polypropylene and 60g benzoyl peroxide (BPO), secondary mixes again, and is warming up at 175 ℃ melting graft reaction 15 minutes, and discharging, cooling, obtains polypropylene ionomer.Through recording maleic acid lanthanum and polyacrylic percentage of grafting, be 1.08%.The apparent morphology observation of SEM is not found agglomerating particles.
Embodiment 4
In Banbury mixer, first drop into 200g maleic acid lanthanum, 40g citric acid and 400g water, at 30 ℃, mix, obtain paste; Drop into 10 kilograms of (10000g) polypropylene and 80g Diisopropyl azodicarboxylate (AIBN), secondary mixes again, and is warming up at 185 ℃ melting graft reaction 10 minutes, and discharging, cooling, obtains polypropylene ionomer.Through recording maleic acid lanthanum and polyacrylic percentage of grafting, be 1.84%.The apparent morphology observation of SEM is not found agglomerating particles.
Embodiment 5
In Banbury mixer, first drop into 300g kilogram of maleic acid lanthanum, 75g oxyacetic acid and 500g water, at 40 ℃, mix, obtain paste; Drop into again the polyolefine that mixes that polypropylene that 10 kilograms (10000g) are 1:1 by weight ratio mixes with polyethylene, and 100g dicumyl peroxide DCP, secondary mixes, and is warming up at 190 ℃ melting graft reaction 7 minutes, discharging, cooling, obtains polyolefin ionomers.Through recording maleic acid lanthanum and polyolefinic percentage of grafting average out to 3.92%.The apparent morphology observation of SEM is not found agglomerating particles.
Embodiment 6
Toward the mixing acid that first drops into oxyacetic acid that 250g maleic acid lanthanum, 50g are 2:1 by weight ratio and pyruvic acid in Banbury mixer and mix, and 300g water, at 30 ℃, mix, obtain paste; Drop into 10 kilograms of (10000g) terpolymer EP rubbers, and 50g dicumyl peroxide (DCP), secondary mixes again, and is warming up at 195 ℃ melting graft reaction 5 minutes, and discharging, cooling, obtains terpolymer EP rubber ionomer.Through recording the percentage of grafting of maleic acid lanthanum and terpolymer EP rubber, be 0.86%.The apparent morphology observation of SEM is not found agglomerating particles.
Comparative example 1
In Banbury mixer, drop into 10 kilograms of (10000g) polyethylene, be warming up at 180 ℃ melting banburying 12 minutes, discharging, cooling, obtains pure polyethylene sample.
Comparative example 2
In Banbury mixer, drop into 10 kilograms of (10000g) polypropylene, be warming up at 175 ℃ melting banburying 15 minutes, discharging, cooling, obtains virgin pp sample.
Comparative example 3
In Banbury mixer, first drop into 200g maleic acid lanthanum, at 35 ℃, stir; Drop into 10 kilograms of (10000g) polyethylene and 50g dicumyl peroxide (DCP), secondary mixes again, and is warming up at 180 ℃ melting graft reaction 12 minutes, and discharging, cooling, obtains polyethylene ionomer.Through recording maleic acid lanthanum and poly percentage of grafting, be 0.41%.The apparent morphology observation of SEM finds that there is obvious agglomerating particles and skewness, mainly because (1) maleic acid lanthanum and poly consistency are poor, both simple blend are easily found to be separated, maleic acid lanthanum is easily reunited, (2) maleic acid lanthanum powder can not melting in grafting process, is therefore just difficult to, with polyolefine, graft reaction occurs on molecular level.
Above-mentioned percentage of grafting is all to measure as follows: in hot xylene solution, after dissolving completely filter gained ionomer sample dissolution (1) with heat filter funnel, get filtrate, by the anti-precipitation of acetone, purifies for three times, and filter cake vacuum-drying is standby; (2) from filter cake, accurately take the 3g sample of purifying, put into retort furnace at 900 ℃ calcination to constant weight; (3) weigh the weight of ash content (lanthanum trioxide) and calculate its mole number and be the amount of substance of grafting maleic acid lanthanum, then be converted into weight; (4) the weight of grafting maleic acid lanthanum obtained to percentage of grafting divided by gross weight (3g).
Choose respectively embodiment 2, embodiment 3 after purifying and comparative example 1, comparative example 2, comparative example 3 samples, and pure maleic acid lanthanum sample, adopt pellet technique to carry out Infrared spectroscopy, result is as shown in Figure 1 and Figure 2.In Fig. 1, A1, B1, C1, D1 curve are respectively maleic acid lanthanum, pure PE(comparative example 1), the infrared spectrum of comparative example 3 and embodiment 2 samples; In Fig. 2, A2, B2, C2 are respectively maleic acid lanthanum, pure PP(comparative example 2) and the infrared spectrum of embodiment 3 samples.As seen from the figure, A1 and A2, C1 and C2 and D1 curve are all at 1544 cm
-1near the stronger absorption peak of appearance, this is the charateristic avsorption band of carboxylate radical, and on pure PE and pure PP curve, there is no this peak, shows under the condition of embodiment 2, embodiment 3 or comparative example 3, all can make maleic acid lanthanum successfully be grafted on polyolefin chain.
Comparing embodiment 2 and comparative example 3, be not difficult to find that their difference is only that embodiment 2 has introduced " 20g oxyacetic acid and 200g water " than comparative example more than 3, but the apparent pattern of the former prepared sample is without agglomerating particles, and the apparent pattern of the prepared sample of the latter has obvious agglomerating particles.This is mainly because maleic acid lanthanum can be dissolved in oxyacetic acid, thereby has greatly improved maleic acid lanthanum and reacted probability with polyethylene on molecular level, and has obviously contained that the reunion of maleic acid lanthanum is inclined to.The percentage of grafting obtaining by embodiment 2 conditions is 0.56%, than percentage of grafting 0.41% height obtaining by comparative example 3 conditions, has also confirmed this point.
Two, the preparation of polycaprolactam/polyolefin ionomers/polyethylene alloy
Embodiment 7
By 10 kilograms of polycaprolactams, 1.5 kilograms of polyethylene, 0.1 kilogram of polypropylene ionomer (pressing embodiment 3 preparations), 0.03 kilogram of antioxidant 1010 mixes at 20 ℃, obtains mixture; Again mixture is placed at 230 ℃ of temperature to melting mixing even, discharging, cooling polycaprolactam/polypropylene ionomer/polyethylene alloy.
Embodiment 8
By 10 kilograms of polycaprolactams, 2.5 kilograms of polyethylene, 0.6 kilogram of polyethylene ionomer (pressing embodiment 2 preparations), 0.06 kilogram is mixed oxidation inhibitor (antioxidant 1010 and 168 mixes by weight 1:1), at 80 ℃, mixes, and obtains mixture; Again mixture is placed at 250 ℃ of temperature to melting mixing even, discharging, cooling polycaprolactam/polypropylene ionomer/polyethylene alloy.
Comparative example 4
By 10 kilograms of polycaprolactams, 1.5 kilograms of polyethylene, 0.03 kilogram of antioxidant 1010 mixes at 20 ℃, obtains mixture; Again mixture is placed at 230 ℃ of temperature to melting mixing even, discharging, cooling polycaprolactam/polyethylene alloy.
Dynamic Rheological Properties test is carried out on U.S. AR-2000 rotational rheometer, and test result as shown in Figure 3, Figure 4.Wherein, A1 and A2 are respectively storage modulus (G') and out-of-phase modulus (G'') curve of polycaprolactam/polyethylene alloy sample in comparative example 4; B1 and B2 are respectively G' and the G'' curve of polycaprolactam/polypropylene ionomer/polyethylene alloy sample of embodiment 7; C1 and C2 are respectively G' and the G'' curve of polycaprolactam/polyethylene ionomer/polyethylene alloy sample of embodiment 8.As seen from the figure, compare with the Binary Alloy System of comparative example 4, if do not consider the impact of sample making course melt temperature, embodiment 7 and embodiment 8 have storage modulus G' and the out-of-phase modulus G'' of the ionomeric ternary alloy system of interpolation in whole range of scanned frequencies all higher, the visco-elasticity that shows ternary alloy system is all better than Binary Alloy System, this has confirmed to introduce polypropylene or polyethylene ionomer can, when improving polycaprolactam/polyethylene binary system viscosity, also improve its melt strength.The increase of melt strength, means that interface binding power strengthens, and polycaprolactam and poly consistency improve.Visible, gained ionomer of the present invention has compatibilization to polycaprolactam/polyethylene binary system, is their desirable compatibilized modifiers.
Claims (10)
1. a polyolefin ionomers, is made 1 by following method) first alcohol ketone acid, maleic acid lanthanum and water are uniformly mixed into paste; 2) paste, initiator and polyolefine are mixed again, and under certain temperature, implement melting graft reaction and make polyolefin ionomers, described alcohol ketone acid has a kind of pyruvic acid, oxyacetic acid, citric acid, oxysuccinic acid of being selected from least.
2. a kind of polyolefin ionomers according to claim 1, is characterized in that
(1) as follows in weight part formula:
A, paste formula are:
Maleic acid lanthanum 100
Alcohol ketone acid 5-25
Water 50-200
The reactant formula of b, polyolefin ionomers is:
Polyolefine 100
Initiator 0.3-1
Paste 1-10;
(2) preparation process is:
Toward processing units, drop into maleic acid lanthanum, alcohol ketone acid and water, at 15-40 ℃, mix, obtain paste; Toward processing units, drop into polyolefine and initiator again, secondary mixes, and at 165-195 ℃ melting graft reaction 5-20 minute, discharging, cooling, obtains polyolefin ionomers.
3. a kind of polyolefin ionomers according to claim 1 and 2, is characterized in that described polyolefine has a kind of polyethylene, polypropylene or polyethylene propylene multipolymer of being selected from least.
4. the preparation method of a kind of polyolefin ionomers according to claim 1 and 2, is characterized in that described initiator is benzoyl peroxide (BPO), dicumyl peroxide (DCP) or azo-bis-isobutyl cyanide (AIBN).
5. the preparation method of a polyolefin ionomers, it is characterized in that: first alcohol ketone acid, maleic acid lanthanum and water are uniformly mixed into paste, again paste, initiator and polyolefine are mixed, and under certain temperature, implement melting graft reaction and make polyolefin ionomers, described alcohol ketone acid has a kind of pyruvic acid, oxyacetic acid, citric acid, oxysuccinic acid of being selected from least.
6. the preparation method of a kind of polyolefin ionomers according to claim 5, is characterized in that
(1) as follows in weight part formula:
A, paste formula are:
Maleic acid lanthanum 100
Alcohol ketone acid 5-25
Water 50-200
The reactant formula of b, polyolefin ionomers is:
Polyolefine 100
Initiator 0.3-1
Paste 1-10;
(2) preparation process is:
Toward processing units, drop into maleic acid lanthanum, alcohol ketone acid and water, at 15-40 ℃, mix, obtain paste; Toward processing units, drop into polyolefine and initiator again, secondary mixes, and at 165-195 ℃ melting graft reaction 5-20 minute, discharging, cooling, obtains polyolefin ionomers.
7. according to the preparation method of a kind of polyolefin ionomers described in claim 5 or 6, it is characterized in that described polyolefine has a kind of polyethylene, polypropylene or polyethylene propylene multipolymer of being selected from least.
8. according to the preparation method of a kind of polyolefin ionomers described in claim 5 or 6, it is characterized in that described initiator is benzoyl peroxide (BPO), dicumyl peroxide (DCP) or azo-bis-isobutyl cyanide (AIBN).
9. the preparation method of a polycaprolactam/polyolefin ionomers/polyethylene alloy, it is characterized in that obtaining as follows: by 100 weight part polycaprolactams, 15-25 weight account polyethylene, described in claim 1-4 or claim 5-8 described in the 1-6 weight part polyolefin ionomers that makes of method, 0.3-0.6 weight part oxidation inhibitor, at 20-80 ℃, mix, obtain mixture; Mixture being placed at 230-250 ℃ of temperature to melting closes and mixes again.
10. the preparation method of a kind of polycaprolactam/polyolefin ionomers/polyethylene alloy according to claim 9, it is characterized in that described oxidation inhibitor has a kind of antioxidant 1010 that is selected from least, antioxidant 1076 or irgasfos 168, or the mixing oxidation inhibitor that mixes of the arbitrary proportion of above-mentioned two kinds of oxidation inhibitor; Described mixing oxidation inhibitor refers to the mixing oxidation inhibitor being mixed by weight 1:1 by antioxidant 1010 and irgasfos 168; The arbitrary described ionomer of claim 1-4 is as the compatibilized modifier application in polycaprolactam/polyethylene binary system.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106674917A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Preparation method of nanotube composite wire containing PBC (Poly Butylene carbonate) |
| CN106674918A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Polyhydroxybutyrate-containing nano-tube composite wire preparation method |
| CN111645374A (en) * | 2020-04-30 | 2020-09-11 | 乐凯胶片股份有限公司 | Transparent polyolefin film for solar cell back plate |
| CN115403904A (en) * | 2022-10-12 | 2022-11-29 | 盐城瑞泽色母粒有限公司 | Biodegradable PBAT color master batch and fiber prepared from same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674917A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Preparation method of nanotube composite wire containing PBC (Poly Butylene carbonate) |
| CN106674918A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Polyhydroxybutyrate-containing nano-tube composite wire preparation method |
| CN111645374A (en) * | 2020-04-30 | 2020-09-11 | 乐凯胶片股份有限公司 | Transparent polyolefin film for solar cell back plate |
| CN115403904A (en) * | 2022-10-12 | 2022-11-29 | 盐城瑞泽色母粒有限公司 | Biodegradable PBAT color master batch and fiber prepared from same |
| CN115403904B (en) * | 2022-10-12 | 2024-01-30 | 盐城瑞泽色母粒有限公司 | Biodegradable PBAT color master batch and fiber prepared from same |
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