JPS5817127A - Production of highly crystalline polyolefin resin foam - Google Patents

Abstract

PURPOSE:To obtain the titled high-expansion ratio foam excellent in heat resistance, flexibility, elasticity, surface appearance and extrusion stability, by extruding a specified propylene/ethylene block copolymer containing a low-boiling organic solvent blowing agent into a low-pressure zone and thereby expanding the copolymer. CONSTITUTION:A propylene/ethylene block copolymer, MI 0.5-2.0, containing 5-15% ethylene component incorporated in the form of block is prepared by polymerizing propylene in the presence of a stereoregular polymerization catalyst and copolymerizing the product with ethylene alone or together with propylene. Then, to 100pts.wt. this copolymer are added 25-40pts.wt. low-boiling organic solvent blowing agent (e.g., dichlorotetrafluoroethane) and 0.1-2pts.wt. nucleating agent (e.g., talc). The mixture is melt-blended in an extruder and then extruder into a low-temperature, low-pressure zone to obtain a high-expansion ratio foam, specific gravity 0.02-0.03.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a foam Va which has greater heat resistance than conventional polyolein foams.

More specifically, a high-crystalline polyolefin resin containing a low-boiling point organic solvent blowing agent is extruded from an extruder into a low-temperature, low-pressure region to produce a foam with a high foaming strength of Xα02 to αOsv. In method i, the monocrystalline polyolefin resin is enriched in ethylene component t5-15% with block KM, melt index J(Ml)$(15-zOtJ7W pyrene).

- Ethylene block copolymer with 69% low-boiling point organic SM using Ditalo I-tet 97-cyloethane as a low-boiling organic SM blooming agent ^ 100 parts by weight of crystalline polyolefin resin vs. 25 to 40 weight tl
SktTsCtot411m and D4II4I! Regarding the V-wrinkle manufacturing method for crystalline polyolefin 2-in resin foam, 70 Jl's focus is on the superior heat resistance ratio of fine crystalline polyolefin 2-in resin, which was conventionally considered to be foam molding. *mv
It is directly foamed by the non-crosslinking extrusion foaming method, and has excellent flexibility, elasticity, and surface beauty, and is excellent in 1q starting and 1 bursting, and shrinks 141 and 211 in the foaming M volatilization after extrusion foaming.
Due to the shrinkage caused by M, there is almost no vh���������������������������� L%.
#M mixture in fip, extruded into a low temperature and low pressure area and foamed directly; non-crosslinked extruded foam ffi is suitable for foam molding, has a relatively wide range of I & wrinkles, and has no am press #1@city molding. 1.In a relatively easy-to-understand factory, most of the foams made from low-crystalline low-tIR polyethylene and non-quality polystyrene are used for insulation, joint materials, and cushioning materials. Is it used for construction?

In addition, due to the nature of the raw material 411 fat, the heat resistance is low, and in practical use the highest tJ point IIL is 100 ° C or less and 69 ° temperature. Pyrolysis #11 Mixing agent, crystalline polyolefin and peroxide in advance
After III, it is formed into a sheet, passed through a heating furnace, and heated.
6. Is there a cross-linked 1III method V battery?

These are just a few steps in the process, and are that much more expensive.

' As for high-temperature use foams, isocyanurated holiclemen 2 ohm and 7 enol 2 ohm, etc., these are very hard types) - υ insulation material for piping systems where the surface is curved or irregularly bent. It could not be applied to the foaming agent and had poor suitability, such as foaming after spraying.Also, it was difficult to apply it to the IIIP machine together with a highly crystalline polyoxysilane 2-in 1v organic solvent additive or a pyrolytic foaming agent. p extrusion specific gravity a
1 to α8 Jim (The method for obtaining IJ foam V is publicly known. The method for producing IJ foam is highly foamed, so it is 1 & 1 less than 1 blowing agent, and the resin with the blowing agent is released from the extruder.) When it comes out of the extruder, it is vaporized by the latent heat of vaporization of the foaming agent, which causes it to foam and maintain its shape when it comes out of the extruder. ′
Since there is less foaming agent υd for L number and - Rahara JIK, press ai
With m yen, υ4ItJIirlQJ machining capacity is small, and due to warping, it can be extruded with 1 p^ (j% foam extrusion Il wrinkle is below 1lI11υ melting point) extruded 几2
Ohm lacks the cooling capacity of the foaming agent υ, so after one foaming, it is molded through a cooling wire or cooling water, or %A is a co-extruded hinge with metal, etc. , extrusion molded by laminating it on other parts. One of them has a denominator called 2Ω and is aimed at structural parts, and the purpose of the present invention is to obtain a high foaming rate with a ratio of less than 03 at sIt%A.
The method is different from that of low-density straight polyethylene and polystyrene f, which have a low softening point, compared to low-crystalline or amorphous resins, which have a low softening point, such as high-density polyethylene and polygoupyrene, which have a low softening point. The crystalline fat melts near the foaming temperature, and the viscoelastic change in the resin O extruded to the low temperature and low pressure region due to ν and crystallization is extremely large. Since the maw surrounding the foam was extremely narrow, it was very difficult to create a foam with a homogeneous structure at magnification. 9. When using a low boiling point organic SM as a blowing agent, if you want to obtain a flexible foam, shrinkage will occur immediately after extrusion foaming, so it is heated and left for several days, which is called thermal aging. mosquito,
Is it said that heating 1 pressure or VH is a method of recovering heating and decompression KlI days? 9. Very crafty! In the highly crystalline mtc, it is almost impossible to restore the 2 ohm that has shrunk to -.

Furthermore, when using rigidity υ large @ Vh * NIk to overcome contraction force, To4 elasticity and flexibility are lost and hard 21
- ζυC stands for urethane 2 ohm manufacturing (t) 64, or a soft 7 ohm with a small functional number Vh (2 to 5) is foamed with an independent hold, and after foaming ffl1, as time υ elapses, it starts to converge. Is there a way to prevent the contraction t' by causing the bubble to rupture just before the end of the air, causing delayed air retention, or to prevent the contraction t' by shrinking the air bubble and crushing the 92 ohm to destroy the air exchange and create continuous air bubbles? K who wants to obtain a foam with such flexibility is ＠／＠
It is absolutely necessary to prevent υ loss after I6ic1
・The present invention addresses the above-mentioned problems by extruding a high-grade material that is excellent in heat resistance, flexibility, elasticity, visceral properties, and excellent extrusion stability, without shrinkage. After careful study with this objective in mind, we have found that a fine-crystalline polyolefin II resin with an extremely low melting point, a goupyrene-ethylene block copolymer, and a certain range of ethylene olefins, are flexible and flexible. Seal or flat? In order to prevent convergence after extrusion, the foam can be produced continuously and stably from the extruder by using a cautious latent medium foaming agent. The obtained product has a heading of 9% U.The present invention is based on the present invention, in which a high-crystalline polyolethane containing a low-boiling point organic bath blowing agent is melted into an extruder in a low-voltage, low-pressure region.
4 and the ratio 1 [Lo 2 ~ α05 (U Takaoki city magnification gJ In the method of manufacturing foam, the crystalline polyolefin tree JIN or the ethylene component thinned by Plutz t5 ~ 15
%, melt index (Ml) is α5~20υ propylene-ethylene block copolymer, p1 dichloronat 220 loethane as a low boiling point organic SS impregnation agent, high crystalline polyolethane 2in information m1ooxts, 25~4
It is a manufacturing method for the highly crystalline polyolefin 2 foamed resin and the propylene used in the non-invention.
l Zeng Yu is in the presence of stereoregular l association interaction υ! 1tLJ 1st
At step 1, add 1 volume of propylene.

On the 142R floor, ethylene or ethylene and 10 birene were added.
4% υ is obtained by multiplying 9 members, and m is the thrust leg V.
Illustrate the fractured surface with a cage microscope! If you guessed it, boriglobilene υ
Sea UGpK Dots and Polyethylene UA Particle Size 10μ~10
Because it has a spherically dispersed structure with 0 μ and a sea-island structure, the globules/-ethylene polymers have a higher elasticity ( II impact resistance) It is rich in K, and its melting point is close to that of ellipropylene, which corresponds to the sea. Noropyrene-ethylene random, which does not have the 0-axis structure f1, has a melting point of both blocks, which is much lower than that of 1 rod. tvT:Toru・Incidentally, based on differential scanning calorimetry (DSC) analysis (melting peaks with a total heat of fusion of more than 100% are polyglopylene homobolymer-15
At 0℃, globylene-ethylene block with 10% ethylene content is 148℃, and ethylene is 6% υglobylene-edelene random compound is 150℃. In addition, as a material for pulling foam/bl blocks with excellent heat resistance, ellipropylene-ethylene block copolymer is considered to be #jll, and Tivoli 1a pyrene homopolymer foam is the winner for its elasticity. Propylene - 2nd and 4th] [4] Because the body has poor heat resistance.

Using a globylene-ethylene block copolymer, a low boiling point organic S medium blowing agent [along with a low boiling point organic S medium blowing agent] is melted and mixed in an extruder, extruded through the extruder into a low temperature and low pressure region, and the specific gravity is α02~(LO3U).
In order to stably produce foams with a foaming ratio of 14, the globylene-ethylene buoyant combination is a lenient admonishment that has certain characteristics. Content 5-15%, melt index (2
30°C 10 minutes ASTM D1238-62T)・Ml
α5~2-OU propylene-ethylene block is a monomer.

As a result of the above range, the propylene-ethylene block copolymer has a relatively low temperature near its melting point, which is outside the range compared to the globylene-ethylene block copolymer. It is medium temperature, 6C and low temperature, high temperature and high pressure O extruder, high temperature and low pressure, low temperature and low pressure region. The vertical range II is wide and has excellent extrusion foaming properties. 0 The ethylene content is rusted in blocks and is 5%19 less.
Foams made from copolymers are not elastic and do not return to their original shape when crushed. Perhaps due to the poor dispersibility of 77Cl birene, it could not be formed tightly with the foaming agent, and the foam could not be maintained while maintaining its shape.
%01lii! It is manufactured from a copolymer of
), melt index (250℃ 10 minutes AST
M D1238-62T) or [L5jl If the to is small, unevenness will occur on the surface, and the product will lose υ. Perhaps because the viscosity was too low, it did not form a foam due to gas leakage. Excellent heat resistance, elasticity, surface 4, excellent extrusion properties, and excellent footing properties. Ratio 31 m [LO2] ~ (Lo3's polyethylene-ethylene foam is obtained by combining polyethylene and ethylene foam, and a more favorable range is the block-bound ethylene content of 8 to 12% Ml. or 1.0-1.5
In comparison to 6,6・b, polypropylene homopolymer can only obtain a hard 2 ohm, and 10-pyrene-ethylenefundum copolymer has very good υ compatibility with the blowing agent. However, it has poor elasticity, and its heat resistance is 150°C for polypropylene homopolymer and 70% birene-ethylene polymer, while 125°C for polypropylene-ethylene polymer copolymer. To-) 90 In the present invention, the block-like rusted ethylene content is not t determined from the mixing ratio of υ10 pyrene/ethylene when heavily stirred, but the infrared absorption of the copolymer actually 6a yield 974 due to globilene in Svetator
effl'''a and around 720 Ca1-'' absorption due to ethylene with WI sweetened according to bootsk.t By baseline method, transmittance (1) v light IIL ratio (r = A tm*/
A -1a ), the ethylene content ("" t+rX1
00%) was calculated.

] Ethylene calculated and added at 1 meeting was 1 time condition, 1 contact time.
Due to the slight difference in wt%, even if the block is 11 Amatai Suga Enzo, - s2 random W1 Juso Koto Kameru o
Cv field excitation infrared absorption spectrum is 731 C11
-' Near 6C absorption or 6 depletion.In the V purpose of the present invention, 2 random units are added to L5] 1 unit rtlIJIIrL)
Since it impairs heat resistance, it is desirable to have as little absorption around 751C1l-'' as possible. Indicated by the ethylene content of 1M!, so aia + yilrz, the above-mentioned infrared a yield spectrum, The ethylene content of 5 to 15%, preferably IL, < u8 to 12%, MI$ [L5 to 20, preferably α8 to 1.5v, is mixed with an organic solvent blowing agent in an extruder.
As mentioned above, by melt-mixing the foam and extruding it into a low-temperature, low-pressure zone using an extruder, a soft, elastic, and smooth foam as shown in Table Ii1 of To9 can be obtained, but in actual manufacturing VC, Dichloronato 220 loethane (20 N 114) is used as an organic solvent blowing agent. Liquid acid %fh is a pressurized liquid used in the evaporation tank. Foaming using ctJ has the following properties: compatibility with lN fat, 11 swelling and gas permeability.In other words, although ctJ has good compatibility with resin, (The bubbles become rough and it is difficult to lower the specific gravity.)
Compatibility %A and resin during foaming I1w! It is a foaming agent that is not mixed with force breathing cL, and it is also 7
The compatibility between the blowing agent and the resin is moderate and the To value is good.

Does the gas permeability of the II tumor affect the yield after foaming? In other words, gas Ua transient V %, gas escapes from the frame to the straw mat and contracts.
8C-cho. - After tυ, 9 ki gradually enters and recovers 4,
Even if the gas permeability to the resin (foaming agent υ permeability) and the air permeability to the resin are close to each other, shrinkage does not occur after 1ilil of v/ri, and the foam fi is released into the gas (foaming agent) in the market or into the atmosphere. Transparent j! It is thought that this is because the air permeates into the bubbles at a rapid rate of 1lIL, and while the gas is being pumped out by 1EF, air is injected into the bubbles and replaced.

The blowing agent that is close to the unexploded 410 pyrene ethylene block and the air permeability Km is dichlorotet I) 7a.
The air permeability/2on 114 transmission ratio was 1.2 when I actually measured it with a 100μ film using Roetan (20mm 114).
1 is 58 methylene chloride t! It becomes 10.

Dichlorotetra 21:I loethane has suitable compatibility with the globylene-ethylene polymer polymer in this @Arc, and has a gas permeability closest to 9, making it suitable for foaming. It is the most practical method because it has good elasticity, can produce fine bubbles, and has a fine structure after ignition.

In the present invention, the number of parts of υdiku cI tetratet 220 loethane blended as a blowing agent is -1100 parts by weight before ti, and -125 to 4 parts by weight after ti.
OJil Miyako is familiar. 25s19 less place! t%
M Peng 1 Foaming agent υ Mixed sol extruded from extrusion AT to low temperature and low pressure zone 7 is evaporated during time 14 Cooling is insufficient and 8 is lost due to foaming ・If there are more than 408, r @ or < rr As a method for producing a 7t-muth using a pyrene-ethylene block copolymer, the preferred range is 30 to 551 Dongjeong. Any method II may be used as long as the frame is a known QJjlK crosslinking extruder/11 method.
After stage υ cow or 2nd stage fungus 〇7su/dar L
V application in the re-cylinder: Press 1 agent into the molten tumor, and extrude 1 tt of N agent into the atmosphere or the depressurized area (IJ cold zone t) and extrude and foam. .

When using two extruders connected together, the screw may be a general full-flight type.Press the foaming agent into the middle of the extruder cylinder or into the extruder cylinder, or into the second book. The extruder is used exclusively for cooling, and the first multi-screw extrusion machine is used to improve consistency and mixability.The method of using a primary multi-screw extrusion machine is to blend the powder with a fine powder that is usually used as a nucleating agent. The masterbatch υm″t″ is loaded into the output machine hopper L. The forming agent and the wall MIυ
To form 5 foaming starting points in the mixed sol, υ41/J't
``A), Normal talc, charcoal calccum, etc. υ Murei imitation powder, sodium citrate V mixture, etc. [for L1 to 21 parts i
In the present invention, it is acceptable to use any substance.
0 pyrene-ethylene block or mixture IL) 5
It is okay to use other 0II fats in combination with other 0II fats that account for 0% or more. 61F fats include high-density, medium-density positive ethylene, and low-density polyethylene I-O. Tactec polyp-pyrene, Atactec polyp-pyrene, polypyrene-ethylene random copolymer, ethylene or propylene-vinyl chloride copolymer 4,
Ethylene or globylene-acrylic sapon ester copolymer, EPDM, polybutadiene, polybutene, ethylene or globylene-sterene co-me form, butadiene-sderene co-me form, axylonitrile-styrene co-me form, salt Accumulated polyethylene% chlorinated polypropylene, etc. 1
几Propylene=Propylene block copolymer 4! Heat stabilizers, antioxidants, ultraviolet absorbers, metal deactivators, lubricants, colorants, antistatic agents, etc. can be added to the body depending on the purpose. In order to carry out the present invention, the foaming agent may be any material having a low boiling point, high steam temperature, and suitable compatibility with resins, halogens, fluorocarbons, etc. system, alkane system υ low boiling point ll
1111k or preferably 1 such as methylene chloride, methyl chloride, trichloromonofluoromethane (Freon 11), dichlorodifuro tetramethane (Freon 12), trichlorotrifluoroethane (Freon IL5), dichlorotet'220
Roetan (Freon 114)-.

Can open gropan, butane, pentane, etc.
iv 2nd 2nd Sagi-t5 Dichloronato 220 loethane (20 N 114) which does not shrink after foaming. As long as there is no shrinkage, it can not be used in combination with the above-mentioned blowing agent. Hereinafter, the present invention will be described in more detail as Practical II/fA and V.
(ASTM D1238-62T), ethylene poverty rate (infrared absorption spectrum A1- by infrared spectroscopy meter RF-
・/ A 174 ↓ 91 tt calculation) Globylene-ethylene block copolymerized resin 1001 was tri-blended with 3 parts of talc α to the neck and fed into the tandem extruder and hopper described below. The 20th extruder (caliber 90allφL/D-24) is equipped with a blowing agent injection hole in the central V position of the metering section, and is equipped with an A11V extruder (caliber 501IIIφL/D=20) and a cylinder equipped with a cooling oil jacket). )k series IIcas
It is composed of gsete.

The first extruder has a screw frame full of 72 liters, and the mts specifications include a feeding section of 150°C, a compression section of 200°C, and a measuring section of 200°C.
The extrusion was carried out at 15kg/brL/C with one screw rotation t-adjusted to 90% dichlorotetra 20loethane as a blowing agent in a bong of 100Ji 1 part resin to 5SXx women, 6 times (t95kg /hr)
The 21st ZJ extrusion screen 1- was supplied to the second extruder through the injection hole Lp press-fitted and the CcD mixed sweetener connecting pipe. Then, the oil jacket υ was heated at a cooling temperature of 130℃ and the 0V mixture was made into a circle with a diameter of 5■φ.

Outer diameter a5B φ'θ Pipe die R is extruded into the atmosphere and the resulting foam is V-shaped 11k as shown in Table 1. 1) Globylene-ethylene combination 'I/L 曾坏v including MI-AI [L5 ~ 20 preferred l, < a (L
8 ~1. 5. Preferably 5 to 15% ethytV rate
# of ia~12%! -The specific gravity is 102 to 105, and the surface has good elasticity and elasticity! You can see that you can get a nice 2tm.

Example 7 and Comparative Examples 7 to 10 Using the same extrusion foaming device as in Table 1, a propylene-ethylene block was prepared with a mass of 1 (M1-1.0! Tele:
/H content 11%), globylene-ethylene random copolymer (M I = 1. 6% hexaterene content),
Polyglobylene homopolymer (Irimectect Polyglobylene MI = 1.0) υ each υ Shinpo υ extrusion opening fl
Sllr row narata. In order to prevent heat decomposition, add the antioxidant bentaerythritatetekkis [5-(5-5-di-t-butyl-4-hydroxy-7-ethyl)]globionate to 11*100 μm of the dobe. The LL3Mk forming agent was dry blended with Merck 15 and %. The press-in type of the starting agent was used under the same binding and temperature conditions as in Table 1. All 3 types were used in the extruder. In the same case, the second extruder oil jacket was cooled at 130°C for the globylene-ethylene block copolymer, 100°C for the globylene-ethylene random gxv body, and polyglobylene homopolymer 135.
After plating at ℃, the obtained 5111 foam υ properties kfi2 are shown in Table 2.
After the eel bottle - the atmosphere of the time when the heat has cooled down - the air pressure table 219 books 91υ Globilene - Ethylene plastic combined with the irises is flexible and elastic, the air bubbles are small, and it is sufficiently heat resistant. ◎J111F18-11 and ratio IIR Examples 9-12 Table 1 M using a double extrusion foaming device
I-1,0 ethylene was tri-blended with 1G% of 10 pyrene-ethylene block AI base t talc tOs ・Blowing agent JI'1tlSK 11 as shown
C4! [
L2 moles were prepared and press-fitted into 4s1 mm.The O-ring V conditions were exactly the same as in Table 1.The resulting foamed foam string had a shrinkage of 11:115 after foaming.Table 5 Cost 51 cyclotitraph v10 ethane (
7 on 114) k As a living body, it is generated IIK. 7 ohm is Qi IIIg - or (extruded bale O does not shrink - 0 etc.

Claims (1)

[Claims] t A high crystalline polyolefin Wam melt containing a low boiling point organic solvent starter is extruded into a low temperature region of an extruder to obtain a mixture with a ratio of 1 [a0
In the method of manufacturing a high expansion ratio V membrane of 2 to aOs, it contains 5 to 15% of a MA polyolefin*TR or an ethylene component refined by a boot process, and has a melt index (Ml) of a5 to 20 liglobylene. Ethylene p4 copolymer body To, t 脣黴 and Ding 4? IIhIja Crystalline polyolefin resin foaming method. 2 JIKU AM TETOTS 70- as a low boiling point organic S catalyst agent
It is claimed that 25 to 40 parts by weight of ethane is added to 100 parts by weight of highly crystalline polyoxysilane resin in accordance with 'Fi'! ! l Section 1 *