CN109867854A - High-strength polyethylene microporous membrane and preparation method thereof - Google Patents
High-strength polyethylene microporous membrane and preparation method thereof Download PDFInfo
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- CN109867854A CN109867854A CN201910223623.8A CN201910223623A CN109867854A CN 109867854 A CN109867854 A CN 109867854A CN 201910223623 A CN201910223623 A CN 201910223623A CN 109867854 A CN109867854 A CN 109867854A
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Abstract
The invention discloses a kind of high-strength polyethylene microporous membranes and preparation method thereof, belong to thin film technique field.High-strength polyethylene microporous membrane of the invention, including the following component according to mass fraction meter: 40 ~ 50 parts of low density linear polyethylene resin, 40 ~ 50 parts of metallocene PE, 10 ~ 13 parts of polypropylene glycol, 6 ~ 9 parts of lubricant, 4 ~ 6 parts of curing agent, 7 ~ 10 parts of modified kaolin.Microporous membrane obtained has excellent tensile strength, breaking strength and tearing strength, meanwhile, porosity reaches 28%.
Description
Technical field
The invention belongs to thin film technique fields, and in particular to a kind of high-strength polyethylene microporous membrane and preparation method thereof.
Background technique
With the development of society, thin film technique using more and more extensive, such as: preservative film, polybag and food packaging
Bag etc., especially food pack, apply the most extensive in market.Some food needs, which are sealed, can just prevent its change
Matter, and some food are then the need to ensure that it has fresh air ventilation, and preservation can not be fully sealed, therefore, microporous membrane is with regard to non-
Often it is suitable for the packaging of this based food.The preparation process of conventional microporous membrane is complex, the bad control of pore size,
And generally for the technical effect for making microporous membrane have ventilation, intensity is often weakened, therefore the two can not be simultaneous
It cares for.However, microporous membrane is in actual use, not needing only to have high intensity should also have ventilatory effect, and therefore, it is necessary to design
One kind having micro-porous permeable performance, and has high-intensitive microporous membrane, meets market actual demand.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind to have micro-porous permeable performance, and has height
The microporous membrane of intensity meets market actual demand.
The present invention adopts the following technical scheme:
High-strength polyethylene microporous membrane, including the following component according to mass fraction meter: low density linear polyethylene tree
40~50 parts of rouge, 40~50 parts of metallocene PE, 10~13 parts of polypropylene glycol, 6~9 parts of lubricant, 4~6 parts of curing agent, change
7~10 parts of kaolin of property.
Further, the modified kaolin includes the following component according to mass fraction meter: 3~7 parts of kaolin, hydroxyl second
4~6 parts of base cellulose, 5~8 parts of Di(dioctylpyrophosphato) ethylene titanate, 2~3 parts of zinc stearate and anhydrous second
30~40 parts of alcohol.
Further, the lubricant is sodium lignin sulfonate, and the curing agent is isophorone diamine.
The preparation method of the high-strength polyethylene microporous membrane, includes the following steps:
Step 1: preparing modified kaolin:
The preparation method of the modified kaolin is specific as follows:
S1, grinding:
According to the mass fraction meter, the kaolin is ground and the kaolin powder that is sieved to obtain；
S2, modification:
According to mass fraction meter, by hydroxyethyl cellulose, Di(dioctylpyrophosphato) ethylene titanate, stearic acid
Kaolin powder obtained by zinc, dehydrated alcohol and S1 and mixing obtain modified kaolin after sieving；
Step 2: mixing:
According to the mass fraction, by the low density linear polyethylene resin, the metallocene PE, poly- the third two
Modified kaolin obtained by alcohol, curing agent, lubricant and step 1 is mixed, and obtains mixture；
Step 3: squeezing out:
It is spare in flakes by screw extruder extruding by mixture obtained by step 2, obtain standby material；
Step 4: biaxial tension:
Standby material obtained by step 3 is subjected to biaxial tension, obtains stretched film, thickness is then measured, trimming, winding, divides
It cuts and packs to get high-strength polyethylene microporous membrane.
Further, when being sieved described in step 1 S1, mesh screen is 800~1000 mesh, and when S2 modifying process, the mixing is stirred
Revolving speed is 300~450r/min when mixing, and revolving speed when being mixed described in step 2 is 300~450r/min.
Further, screw extruder described in step 3 is divided into five temperature sections, is respectively as follows: the first bringing-up section 70~80
DEG C, the second 80~120 DEG C of bringing-up section, 120~160 DEG C of third bringing-up section, the 4th 160~190 DEG C of bringing-up section, the 5th bringing-up section
190~220 DEG C.
Further, in step 4 biaxial orientation process, draw ratio is 2~4%, and micropore gap is 0.4~0.9 μm.
Compared with the prior art, the present invention has the following beneficial effects:
The first, microporous membrane of the invention is made by the mixing of low density linear polyethylene resin complex metallocene PE
With, not only save the cost, meanwhile, and the polypropylene glycol with toughening effect is used in mixed way, and helps to overcome by pure polyethylene
The low defect of film strength obtained prevents from preventing film breaks in subsequent biaxial tension.Also, in order to further ensure thin
The stability of film prevents that local fracture occurs in biaxial tension, and research staff is by adding modified kaolin, so that system
The microporous membrane obtained has excellent tensile strength and breaking strength to guarantee that the preparation section of entire microporous membrane is smooth, and
It ensure that its quality；
The second, kaolin is by the way that after 800~1000 mesh mesh screens, partial size is minimum, passes through bis- (two octyloxy pyrophosphates
Base) ethylene titanate esters are modified kaolin powder, then pass through the hydroxyethyl cellulose that will play filming function and have and divide
After the zinc stearate and the kaolin mixing that dissipate effect, thin film strength can effectively improve, prevent the appearance part when stretching disconnected
The case where splitting improves yield rate, has saved cost.
Specific embodiment
Raw material used in the present invention is commercially available product, in which:
Di(dioctylpyrophosphato) ethylene titanate is purchased from Guangzhou Zhong Jie Chemical Industry Science Co., Ltd.
Embodiment 1
High-strength polyethylene microporous membrane, including the following component according to mass fraction meter: low density linear polyethylene tree
40 parts of rouge, 40 parts of metallocene PE, 10 parts of polypropylene glycol, 6 parts of lubricant, 4 parts of curing agent, 7 parts of modified kaolin.
The modified kaolin includes the following component according to mass fraction meter: 3 parts of kaolin, 4 parts of hydroxyethyl cellulose,
5 parts of Di(dioctylpyrophosphato) ethylene titanate, 2 parts and 30 parts of dehydrated alcohol of zinc stearate.
Wherein, the lubricant is sodium lignin sulfonate, and the curing agent is isophorone diamine.
The preparation method of the high-strength polyethylene microporous membrane, includes the following steps:
Step 1: preparing modified kaolin:
The preparation method of the modified kaolin is specific as follows:
S1, grinding:
According to the mass fraction meter, the kaolin is ground and the kaolin powder that is sieved to obtain, when the sieving, mesh screen
For 800 mesh；
S2, modification:
According to mass fraction meter, by hydroxyethyl cellulose, Di(dioctylpyrophosphato) ethylene titanate, stearic acid
Kaolin powder obtained by zinc, dehydrated alcohol and S1 is mixed, after sieving modified kaolin, revolving speed is when the mixing
300r/min, when the sieving, mesh screen is 800 mesh.
Step 2: mixing:
According to the mass fraction, by the low density linear polyethylene resin, the metallocene PE, poly- the third two
Alcohol, curing agent, modified kaolin is mixed obtained by lubricant and step 1, and the revolving speed when mixing is 300r/
Min is to get mixture.
Step 3: squeezing out:
It is spare in flakes by screw extruder extruding by mixture obtained by step 2, obtain standby material；
Wherein, the screw extruder is divided into five temperature sections, is respectively as follows: 70 DEG C of the first bringing-up section, the second bringing-up section 80
DEG C, 120 DEG C of third bringing-up section, the 4th 160 DEG C of bringing-up section, the 5th 190 DEG C of bringing-up section.
Step 4: biaxial tension:
Standby material obtained by step 3 is subjected to biaxial tension, obtains stretched film, thickness is then measured, trimming, winding, divides
It cuts and packs to get high-strength polyethylene microporous membrane；
In the biaxial orientation process, draw ratio 2%, micropore gap is 0.4 μm.
Embodiment 2
High-strength polyethylene microporous membrane, including the following component according to mass fraction meter: low density linear polyethylene tree
42 parts of rouge, 42 parts of metallocene PE, 11 parts of polypropylene glycol, 7 parts of lubricant, 5 parts of curing agent, 8 parts of modified kaolin.
The modified kaolin includes the following component according to mass fraction meter: 4 parts of kaolin, 5 parts of hydroxyethyl cellulose,
6 parts of Di(dioctylpyrophosphato) ethylene titanate, 2 parts and 33 parts of dehydrated alcohol of zinc stearate.
Wherein, the lubricant is sodium lignin sulfonate, and the curing agent is isophorone diamine.
The preparation method of the high-strength polyethylene microporous membrane, includes the following steps:
Step 1: preparing modified kaolin:
The preparation method of the modified kaolin is specific as follows:
S1, grinding:
According to the mass fraction meter, the kaolin is ground and the kaolin powder that is sieved to obtain, when the sieving, mesh screen
For 850 mesh；
S2, modification:
According to mass fraction meter, by hydroxyethyl cellulose, Di(dioctylpyrophosphato) ethylene titanate, stearic acid
Kaolin powder obtained by zinc, dehydrated alcohol and S1 is mixed, after sieving modified kaolin, the revolving speed when mixing
For 350r/min, when the sieving, mesh screen is 850 mesh.
Step 2: mixing:
According to the mass fraction, by the low density linear polyethylene resin, the metallocene PE, poly- the third two
Alcohol, curing agent, modified kaolin is mixed obtained by lubricant and step 1, and revolving speed is 350r/min when the mixing,
Up to mixture.
Step 3: squeezing out:
It is spare in flakes by screw extruder extruding by mixture obtained by step 2, obtain standby material；
Wherein, the screw extruder is divided into five temperature sections, is respectively as follows: 72 DEG C of the first bringing-up section, the second bringing-up section 90
DEG C, 130 DEG C of third bringing-up section, the 4th 170 DEG C of bringing-up section, the 5th 200 DEG C of bringing-up section.
Step 4: biaxial tension:
Standby material obtained by step 3 is subjected to biaxial tension, obtains stretched film, thickness is then measured, trimming, winding, divides
It cuts and packs to get high-strength polyethylene microporous membrane；
In the biaxial orientation process, draw ratio 3%, micropore gap is 0.5 μm.
Embodiment 3
High-strength polyethylene microporous membrane, including the following component according to mass fraction meter: low density linear polyethylene tree
45 parts of rouge, 45 parts of metallocene PE, 12 parts of polypropylene glycol, 8 parts of lubricant, 6 parts of curing agent, 9 parts of modified kaolin.
The modified kaolin includes the following component according to mass fraction meter: 5 parts of kaolin, 6 parts of hydroxyethyl cellulose,
7 parts of Di(dioctylpyrophosphato) ethylene titanate, 3 parts and 35 parts of dehydrated alcohol of zinc stearate.
Wherein, the lubricant is sodium lignin sulfonate, and the curing agent is isophorone diamine.
The preparation method of the high-strength polyethylene microporous membrane, includes the following steps:
Step 1: preparing modified kaolin:
The preparation method of the modified kaolin is specific as follows:
S1, grinding:
According to the mass fraction meter, the kaolin is ground and the kaolin powder that is sieved to obtain, when the sieving, mesh screen
For 900 mesh；
S2, modification:
According to mass fraction meter, by hydroxyethyl cellulose, Di(dioctylpyrophosphato) ethylene titanate, stearic acid
Zinc, dehydrated alcohol and mixing, after sieving modified kaolin, the revolving speed when mixing is 400r/min, described
When sieving, mesh screen is 900 mesh.
Step 2: mixing:
According to the mass fraction, by the low density linear polyethylene resin, the metallocene PE, poly- the third two
Alcohol, curing agent, modified kaolin is mixed obtained by lubricant and step 1, and the revolving speed when mixing is 400r/
Min is to get mixture.
Step 3: squeezing out:
It is spare in flakes by screw extruder extruding by mixture obtained by step 2, obtain standby material；
Wherein, the screw extruder is divided into five temperature sections, is respectively as follows: 75 DEG C of the first bringing-up section, the second bringing-up section 110
DEG C, 150 DEG C of third bringing-up section, the 4th 180 DEG C of bringing-up section, the 5th 210 DEG C of bringing-up section.
Step 4: biaxial tension:
Standby material obtained by step 3 is subjected to biaxial tension, obtains stretched film, thickness is then measured, trimming, winding, divides
It cuts and packs to get high-strength polyethylene microporous membrane；
In the biaxial orientation process, draw ratio 4%, micropore gap is 0.6 μm.
Embodiment 4
High-strength polyethylene microporous membrane, including the following component according to mass fraction meter: low density linear polyethylene tree
50 parts of rouge, 50 parts of metallocene PE, 13 parts of polypropylene glycol, 9 parts of lubricant, 6 parts of curing agent, 10 parts of modified kaolin.
The modified kaolin includes the following component according to mass fraction meter: 7 parts of kaolin, 6 parts of hydroxyethyl cellulose,
8 parts of Di(dioctylpyrophosphato) ethylene titanate, 3 parts and 40 parts of dehydrated alcohol of zinc stearate.
Wherein, the lubricant is sodium lignin sulfonate, and the curing agent is isophorone diamine.
The preparation method of the high-strength polyethylene microporous membrane, includes the following steps:
Step 1: preparing modified kaolin:
The preparation method of the modified kaolin is specific as follows:
S1, grinding:
According to the mass fraction meter, the kaolin is ground and the kaolin powder that is sieved to obtain, it is described when being ground up, sieved,
Mesh screen is 1000 mesh；
S2, modification:
According to mass fraction meter, by hydroxyethyl cellulose, Di(dioctylpyrophosphato) ethylene titanate, stearic acid
Kaolin powder obtained by zinc, dehydrated alcohol and S1 is mixed, after sieving modified kaolin, the revolving speed when mixing
For 450r/min, when the sieving, mesh screen is 1000 mesh.
Step 2: mixing:
According to the mass fraction, by modified kaolin obtained by step 1 and the low density linear polyethylene resin, institute
Metallocene PE, polypropylene glycol, curing agent and mix lubricant stirring are stated, revolving speed is 450r/min when the mixing,
Up to mixture.
Step 3: squeezing out:
It is spare in flakes by screw extruder extruding by mixture obtained by step 2, obtain standby material；
Wherein, the screw extruder is divided into five temperature sections, is respectively as follows: 80 DEG C of the first bringing-up section, the second bringing-up section 120
DEG C, 160 DEG C of third bringing-up section, the 4th 190 DEG C of bringing-up section, the 5th 220 DEG C of bringing-up section.
Step 4: biaxial tension:
Standby material obtained by step 3 is subjected to biaxial tension, obtains stretched film, thickness is then measured, trimming, winding, divides
It cuts and packs to get high-strength polyethylene microporous membrane；
In the biaxial orientation process, draw ratio 4%, micropore gap is 0.9 μm.
Reference examples 1
High-strength polyethylene microporous membrane, including the following component according to mass fraction meter: low density linear polyethylene tree
50 parts of rouge, 50 parts of metallocene PE, 13 parts of polypropylene glycol, 9 parts of lubricant, 6 parts of curing agent.
Wherein, the lubricant is sodium lignin sulfonate, and the curing agent is isophorone diamine.
The preparation method of the high-strength polyethylene microporous membrane, includes the following steps:
Step 1: mixing:
According to the mass fraction, by the low density linear polyethylene resin, the metallocene PE, poly- the third two
Alcohol, curing agent and mix lubricant stirring, the revolving speed when mixing are 450r/min to get mixture.
Step 2: squeezing out:
It is spare in flakes by screw extruder extruding by mixture obtained by step 1, obtain standby material；
Wherein, the screw extruder is divided into five temperature sections, is respectively as follows: 80 DEG C of the first bringing-up section, the second bringing-up section 120
DEG C, 160 DEG C of third bringing-up section, the 4th 190 DEG C of bringing-up section, the 5th 220 DEG C of bringing-up section.
Step 3: biaxial tension:
Standby material obtained by step 2 is subjected to biaxial tension, obtains stretched film, thickness is then measured, trimming, winding, divides
It cuts and packs to get high-strength polyethylene microporous membrane；
In the biaxial orientation process, draw ratio 4%, micropore gap is 0.9 μm.
Performance detection is carried out by Examples 1 to 4 and to the resulting microporous membrane of reference examples 1, testing result such as the following table 1:
Wherein:
According to GB/T 13519-2016 be packed for polytene thermal-shrinkable film measurement tensile strength, elongation at break and
Angle tear strength；
The testing result of 1 Examples 1 to 4 of table and the resulting EVA micelle modified elastomer of reference examples 1
As can be known from Table 1, the porosity of microporous membrane made from Examples 1 to 4 reaches 28%, and tensile strength reaches longitudinal
30Mpa, lateral 27Mpa, elongation at break reaches longitudinal 225Mpa, lateral 415Mpa, and tearing strength reaches 101g, elongates
Intensity when 50% reaches 423g/25mm.On the contrary, without addition modified kaolin in reference examples 1, microporous membrane obtained exists
It is weaker than microporous membrane made from Examples 1 to 4 in tensile strength, breaking strength and tear strength properties, and porosity is also small
The microporous membrane made from Examples 1 to 4, it can be seen that, it is thin that modified kaolin through the invention can effectively improve micropore
The porosity and its intensity of film.
It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, above-described embodiment and explanation
It is merely illustrated the principles of the invention described in book, without departing from the spirit and scope of the present invention, the present invention also has
Various changes and modifications, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention
It is defined by the appending claims and its equivalent thereof.
Claims (7)
1. high-strength polyethylene microporous membrane, which is characterized in that including the following component according to mass fraction meter: low-density is linear
40 ~ 50 parts of polyvinyl resin, 40 ~ 50 parts of metallocene PE, 10 ~ 13 parts of polypropylene glycol, 6 ~ 9 parts of lubricant, curing agent 4 ~ 6
Part, 7 ~ 10 parts of modified kaolin.
2. high-strength polyethylene microporous membrane according to claim 1, which is characterized in that the modified kaolin includes pressing
According to the following component of mass fraction meter: 3 ~ 7 parts of kaolin, 4 ~ 6 parts of hydroxyethyl cellulose, bis- (two octyloxy pyrophosphoric acid ester groups) second
5 ~ 8 parts of titanate esters of support, 2 ~ 3 parts and 30 ~ 40 parts of dehydrated alcohol of zinc stearate.
3. high-strength polyethylene microporous membrane according to claim 1, which is characterized in that the lubricant is sulfomethylated lignin
Sour sodium, the curing agent are isophorone diamine.
4. the preparation method of high-strength polyethylene microporous membrane as claimed in claim 2, which comprises the steps of:
Step 1: preparing modified kaolin:
The preparation method of the modified kaolin is specific as follows:
S1, grinding:
According to the mass fraction meter, the kaolin is ground and the kaolin powder that is sieved to obtain；
S2, modification:
According to mass fraction meter, by hydroxyethyl cellulose, Di(dioctylpyrophosphato) ethylene titanate, zinc stearate,
Dehydrated alcohol and S1 gained kaolin powder are mixed, and modified kaolin is obtained after sieving；
Step 2: mixing:
According to the mass fraction, by the low density linear polyethylene resin, the metallocene PE, polypropylene glycol, consolidate
Modified kaolin obtained by agent, lubricant and step 1 is mixed, and obtains mixture；
Step 3: squeezing out:
It is spare in flakes by screw extruder extruding by mixture obtained by step 2, obtain standby material；
Step 4: biaxial tension:
Standby material obtained by step 3 is subjected to biaxial tension, obtains stretched film, then measure thickness, trimming, winding, cutting and
Packaging is to get high-strength polyethylene microporous membrane.
5. the preparation method of high-strength polyethylene microporous membrane according to claim 4, which is characterized in that step 1 S1 institute
When stating sieving, mesh screen is 800 ~ 1000 mesh, and in S2 modifying process, the revolving speed when mixing is 300 ~ 450r/min, S2
When sieving, mesh screen is 800 ~ 1000 mesh, and revolving speed when being mixed described in step 2 is 300 ~ 450r/min.
6. the preparation method of high-strength polyethylene microporous membrane according to claim 4, which is characterized in that described in step 3
Screw extruder is divided into five temperature sections, is respectively as follows: 70 ~ 80 DEG C of the first bringing-up section, the second 80 ~ 120 DEG C of bringing-up section, third heating
120 ~ 160 DEG C of section, the 4th 160 ~ 190 DEG C of bringing-up section, the 5th 190 ~ 220 DEG C of bringing-up section.
7. the preparation method of high-strength polyethylene microporous membrane according to claim 4, which is characterized in that described in step 4
In biaxial orientation process, draw ratio is 2 ~ 4%, and micropore gap is 0.4 ~ 0.9 μm.
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