CN108239347A - A kind of method for inhibiting isotactic poly-1-butylene crystal form II-I transformations by being blended with low density polyethylene (LDPE) - Google Patents
A kind of method for inhibiting isotactic poly-1-butylene crystal form II-I transformations by being blended with low density polyethylene (LDPE) Download PDFInfo
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- CN108239347A CN108239347A CN201611228196.5A CN201611228196A CN108239347A CN 108239347 A CN108239347 A CN 108239347A CN 201611228196 A CN201611228196 A CN 201611228196A CN 108239347 A CN108239347 A CN 108239347A
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- butylene
- density polyethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The invention discloses a kind of methods for inhibiting the poly- 1 butylene crystal form II I transformations of isotactic by being blended with low density polyethylene (LDPE), it is blended using low density polyethylene (LDPE) and poly- 1 butylene of homopolymerization isotactic, it was found that the crystal form II I transformations of 1 B of iP are significantly more slack-off than pure 1 B crystal form II I of iP transformations in 1 B/LDPE of iP blending samples, show that LDPE blendings inhibit the crystal transfer of 1 B of iP.The present invention uses relatively simple technical process, can effectively inhibit the transformation of crystal form.
Description
Technical field
The invention belongs to technical field of polymer processing, more particularly, it is brilliant to be related to a kind of inhibition isotactic poly-1-butylene
The method of type II-I transformations.
Background technology
Isotactic poly-1-butylene (iP-1-B) is widely used in the sealing material of hot-water line, synthetic fibers, food and medical supplies
The industrial circles such as feed additives as a kind of semicrystalline polyolefins, have prominent creep resistance, impact resistance, chemically-resistant
Property, environmental stress crack resistance and the high advantage of heat distortion temperature.IP-1-B has complicated polymorphic structures, at different conditions
Crystallization forms five kinds of I, II, III, I ', II ' different crystal forms, and melt crystallization forms the crystal form II of tetragonal crystal system, and strand uses
Pairs of 113Helical conformation is piled up, and significantly internal molecular motion is maintain more than glass transition temperature 249K, and melting enthalpy is
62.5J·g-1, density 0.902gcm-3, fusing point is 110-120 DEG C.Metastable crystal form II is gradually converted at room temperature
Hexagonal crystal crystal form I, strand is using 3 more closely piled up1Helical conformation, melting enthalpy 141.1Jg-1, density is
0.951g·cm-3.Crystal form II-I changes hardness, tensile strength, fusing point and the density that can increase iP-1-B, while can also be because of crystallization
The slow transformation of structure causes the contraction of material or product, the characteristics of in this change procedure so that iP-1-B may obtain spy
Different practical application.
The prior art shows that the change of iP-1-B strand features influences crystal form II-I conversion rates, such as average molecular matter
Amount, isotacticity, comonomer containing amount and type etc., can promote iP-1-B's by changing iP-1-B molecular chain structures feature
II-I changes, some other can promote effect of the technology that the II-I of iP-1-B changes there are also report, such as applied force, and
Can be that the technology that potential special-purpose delays the II-I of iP-1-B to change seldom reports that Turner-Jones is once by a large amount of
Research finds that crystal form II-I conversion rates can be regulated and controled by 1- butylene and 1- alkane random copolymerizations, such as with more than 5 carbon originals
Linear 1- alkane and the branched monomer copolymerization of son can inhibit crystal form II-I to change, and can then add with ethylene, propylene, the copolymerization of 1- amylenes
Fast crystal transfer.But random copolymerization has crystallization process inhibiting effect and influences final crystal habit, it will usually reduce crystallization
Degree forms thermal stability and low-melting smaller crystal, common no matter from the angle for promoting or delaying the II-I of iP-1-B to crystallize
It is poly- to show condition harshness, react limitation of the complicated, polymerization process there are solvent.Blending and modifying by by two or more
The advantages of different high molecular materials is combined into a new material, this new material combines each component, and it is easy to operate, it can
Batch production, is used widely in commercial Application.Low density polyethylene (LDPE) (LDPE) is as a kind of thermoplasticity cheap and easy to get
Plastics, for packing, building, industrial, agriculture and consumer goods market, the molecular structure of LDPE is using branched side chain as main spy
Sign, it makes LDPE films have flexibility, the transparency and easily processed into type.If crystal form II-I can be inhibited to change, will not deposit
In the change of mechanical property, the generation for the problems such as not having density of material, fusing point, dimensional contraction.
Invention content
Inhibit under relatively simple experiment condition it is an object of the invention to overcome the deficiencies of the prior art and provide one kind
The method that iP-1-B crystal forms II changes to crystal form I, based on relatively simple polymer blended, by by iP-1-B and LDPE according to
Certain ratio blending, a kind of method that relative ease is provided effectively to inhibit or delay again the II-I of iP-1-B to change are
The potential application of function of iP-1-B provides technological approaches.
The technical purpose of the present invention is achieved by following technical proposals：
A kind of method for inhibiting isotactic poly-1-butylene crystal form II-I transformations by being blended with low density polyethylene (LDPE), using low close
Degree polyethylene is blended with isotactic poly-1-butylene, and isotactic poly-1-butylene is homopolymer, is gathered by low density polyethylene (LDPE) and isotactic
In the blend of 1- butylene composition, the mass percent of low density polyethylene (LDPE) for 0-15wt% and not equal to zero, i.e. gather by low-density
Ethylene mass/(low density polyethylene (LDPE)+isotactic poly-1-butylene) quality sum.
In the above-mentioned technical solutions, the mass percent of low density polyethylene (LDPE) is 5-10wt%.
In the above-mentioned technical solutions, low density polyethylene (LDPE) and isotactic poly-1-butylene melting are realized on torque rheometer altogether
Mixed, melting temperature is 150-220 DEG C, and 0.5mm then is made by melting compression molding on laboratory self-control vulcanizing press
Thick sheet sample, the molding temperature specifically used can be 170-180 DEG C, after 8-10min is preheated, pressurize and rise to 20-
25MPa after keeping 3-5min, is cold-pressed 8-10min under 20-25MPa, and obtained print is spare.
In the above-mentioned technical solutions, the print after low density polyethylene (LDPE) and isotactic poly-1-butylene blending is being placed at room temperature for,
So that the II crystalline substances formed are changed into I crystalline substances, standing time is 25-30 days.
In the above-mentioned technical solutions, the print after the low density polyethylene (LDPE) of I crystalline substances and isotactic poly-1-butylene blending is translated into
The disk of a diameter of 10mm is cut into, using linkam thermal station temperature controls, 200-220 are warming up to 3-5 DEG C/min of heating rate
DEG C) and keep the temperature 3-5min, make the brilliant all meltings of I that it contains, then with 10-15 DEG C/that min cools to room temperature 20-25 is Celsius
Degree, sample crystallization form II crystalline substances, are stored at room temperature, and change behavior using X-ray diffraction (XRD) observation iP-1-B crystal forms II-I,
An XRD was surveyed every 1 hour, tracks its crystal form II-I transition processes, it is bright that crystal form II-I transformations in iP-1-B samples can be observed
It is aobvious to receive inhibition.
Technical method provided by the invention is applicable to homopolymerization iP-1-B, in general, from melt decrease temperature crystalline,
The metastable II crystalline substances of thermodynamics will be obtained, being changed into thermodynamically stable I crystalline substances needs the long period, and uses provided by the invention
Technical method can inhibit this transition process, and method is simple.Compared with prior art, the present invention provides a kind of inhibition iP-1-B
The method of crystal form II-I transformations, it is simple for process, melt blending is carried out by different content LDPE and iP-1-B, is tracked using XRD
Its crystal form II-I transition processes, the addition of LDPE have changed inhibiting effect, i.e. low density polyethylene (LDPE) to the crystal form II-I of iP-1-B
Application in the crystal form II-I transformations for inhibiting isotactic poly-1-butylene (iP-1-B) is realized by the two blending method and inhibits to make
With wherein isotactic poly-1-butylene is homopolymerization isotactic poly-1-butylene.
Description of the drawings
Fig. 1 be in the embodiment of the present invention iP-1-B 0110M in 20-25 degrees Celsius of lower II-I transition processes of room temperature
XRD curves.
Fig. 2 is 15wt%LDPE is added in the embodiment of the present invention iP-1-B 0110M at room temperature in II-I transition processes
XRD curves.
Fig. 3 is that iP-1-B 0110M and iP-1-B 0110M/LDPE (85/15) II-I turns at room temperature in the embodiment of the present invention
Change process contrast curve.
Specific embodiment
The technical solution further illustrated the present invention with reference to specific embodiment.
Weigh 50g iP-1-B 0110M (Basell companies, homopolymerization iP-1-B, the trade mark be PB 0110M, Mw=
711000g/mol, Tm=117 DEG C, Tg=-20 DEG C, ρ=0.914gcm-3, melt flow rate (MFR) is 0.4g/10min (190
DEG C/2.16kg)) (Beijing Yanshan Petrochemical, trade mark 112A-1, MFR=2.0g/min are close with the LDPE 112A-1 of 8.8235g
It spends for 0.918g/cm3), after being pre-mixed uniformly, in XSS-30 type torque rheometers, 12min, rotating speed are blended at 180 DEG C
For 30rpm, obtain the iP-1-B/LDPE blends of 15wt%LDPE contents, be denoted as iP-1-B/LDPE (85/15, i.e. LDPE's
Add in the ratio of quality and iP-1-B+LDPE quality sums), gained sample is cooled to room temperature rear spare.
7g iP-1-B and 7g iP-1-B/LDPE (85/15) are preheated into 10min at 180 DEG C with vulcanizing press respectively, with
Pressure is gradually increased to 25MPa by the way of gradually pressurizeing afterwards, 3min is kept the temperature under maximum pressure, is then cold-pressed under 25MPa
8min presses the sheet sample for 0.5mm thickness, and 20-25 degrees Celsius of room temperature places 30 days (24 × 30 hours) after taking-up, makes II brilliant
Fundamental transformation is entirely I crystalline substances；Two kinds of samples are cut into 1mm long 1mm wide respectively, are wrapped up with individual layer aluminium foil, using linkam thermal station
With 10 DEG C/min from room temperature to 200 DEG C, 3min is kept；Room temperature is cooled to 15 DEG C/min again, i.e. the brilliant all meltings of I are dropped again
It crystallizes to form II crystalline substances to RT sample.
Sample is stood for 20-25 degrees Celsius in room temperature, carries out XRD tests to sample at regular intervals, and tracking iP-1-B is brilliant
Type II-I transition processes, scanning range are 5-30 °, each sample used time 10min, and the relative amount of crystal form I is used in transition process
Crystal form I proportion f in crystal form I and crystal form II1It determines, by (110) of 2 θ=9.9 ° in XRD diffracting spectrumsICrystal face and in 2 θ
=11.9 ° of (200)IIThe ratio of crystal face is calculated, such as：
I (110) in equationIWith I (200)II(110) of 2 θ=9.9 ° in XRD spectrum are represented respectivelyIWith 2 θ=11.9 °
(200)IICrystal face intensity (i.e. diffraction peak areas).
Fig. 1 is pure iP-1-B 0110M crystal transfer curves at room temperature, Fig. 2 for iP-1-B/LDPE (85/15) at room temperature with
The crystal transfer curve that time increases, at room temperature increase at any time, crystal form II diffraction area are reduced, and crystal form I diffraction area increases
Add；Fig. 3 is accounted for (110) for diffraction peak areas of the crystal form I at (110) crystal faceI(200)IIDiffraction peak areas ratio, can see
Go out iP-1-B conversion rates in iP-1-B/LDPE (85/15) significantly to slow down, have apparent inhibiting effect to crystal form II-I transformations,
Significantly lower than the sample not being blended.
The blending ratio of adjustment iP-1-B and LDPE is recorded according to the content of present invention, according to identical technological parameter and test
Condition, the iP-1-B conversion rates that can find to be blended with LDPE significantly inhibit, less than the sample of not blended processing.It is right above
The present invention has done illustrative description, it should explanation, in the case of the core for not departing from the present invention, and any simple change
Shape, modification or other skilled in the art can not spend the equivalent replacement of creative work to each fall within protection of the invention
Range.
Claims (6)
1. a kind of method for inhibiting isotactic poly-1-butylene crystal form II-I transformations by being blended with low density polyethylene (LDPE), feature exist
In being blended using low density polyethylene (LDPE) and isotactic poly-1-butylene, isotactic poly-1-butylene is homopolymer, by low density polyethylene
In the blend that alkene is formed with isotactic poly-1-butylene, the mass percent of low density polyethylene (LDPE) is for 0-15wt% and not equal to zero.
It is 2. according to claim 1 a kind of by the way that II-I turns of inhibition isotactic poly-1-butylene crystal form is blended with low density polyethylene (LDPE)
The method of change, which is characterized in that the mass percent of low density polyethylene (LDPE) is 5-10wt%.
3. according to described in claims 1 or 2 a kind of by the way that inhibition isotactic poly-1-butylene crystal form is blended with low density polyethylene (LDPE)
The method of II-I transformations, which is characterized in that low density polyethylene (LDPE) and isotactic poly-1-butylene melting are realized on torque rheometer altogether
Mixed, melting temperature is 150-220 DEG C.
4. application of the low density polyethylene (LDPE) in the crystal form II-I transformations for inhibiting isotactic poly-1-butylene, which is characterized in that pass through two
Person's blending method realizes inhibiting effect, and wherein isotactic poly-1-butylene is homopolymerization isotactic poly-1-butylene.
5. low density polyethylene (LDPE) according to claim 4 answering in the crystal form II-I transformations for inhibiting isotactic poly-1-butylene
With, which is characterized in that in the blend being made of low density polyethylene (LDPE) and isotactic poly-1-butylene, the quality of low density polyethylene (LDPE)
Percentage is for 0-15wt% and not equal to zero, preferably 5-10wt%.
6. low density polyethylene (LDPE) according to claim 4 answering in the crystal form II-I transformations for inhibiting isotactic poly-1-butylene
With, which is characterized in that realize that low density polyethylene (LDPE) and isotactic poly-1-butylene melt blending, melting temperature are on torque rheometer
150-220℃。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611228196.5A CN108239347B (en) | 2016-12-27 | 2016-12-27 | Method for inhibiting isotactic poly-1-butylene crystal form II-I conversion by blending with low-density polyethylene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611228196.5A CN108239347B (en) | 2016-12-27 | 2016-12-27 | Method for inhibiting isotactic poly-1-butylene crystal form II-I conversion by blending with low-density polyethylene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978515A (en) * | 2006-11-30 | 2007-06-13 | 程振中 | Modifier for 1-butene homopolyener and 1-butene and other alpha-olefin copolymer |
| CN103951898A (en) * | 2014-04-12 | 2014-07-30 | 青岛科技大学 | Poly 1-butene/1-butylene-propylene copolymer in-reactor alloy and preparation method thereof |
| CN104610669A (en) * | 2015-02-15 | 2015-05-13 | 青岛科技大学 | Polyolefin alloy material and preparation method thereof |
-
2016
- 2016-12-27 CN CN201611228196.5A patent/CN108239347B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978515A (en) * | 2006-11-30 | 2007-06-13 | 程振中 | Modifier for 1-butene homopolyener and 1-butene and other alpha-olefin copolymer |
| CN103951898A (en) * | 2014-04-12 | 2014-07-30 | 青岛科技大学 | Poly 1-butene/1-butylene-propylene copolymer in-reactor alloy and preparation method thereof |
| CN104610669A (en) * | 2015-02-15 | 2015-05-13 | 青岛科技大学 | Polyolefin alloy material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FIORENZA AZZURRI等: "Polymorphic Transformation in Isotactic 1-Butene/Ethylene Copolymers", 《MACROMOLECULES》 * |
| HUILONG GUO等: "Deformation-induced crystalline structure evolutions of isotactic poly-1-butene", 《COLLOID AND POLYMER SCIENCE》 * |
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Address after: 300452 Binhai Industrial Research Institute Campus of Tianjin University, No. 48 Jialingjiang Road, Binhai New Area, Tianjin Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |