CN103834097B - A kind of polypropylene microparticle and method for making and the method being prepared polypropylene foaming beads by it and product - Google Patents
A kind of polypropylene microparticle and method for making and the method being prepared polypropylene foaming beads by it and product Download PDFInfo
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Abstract
The present invention relates to a kind of polypropylene microparticle and preparation method thereof and the method being prepared polypropylene foaming beads by it and product.Described polypropylene microparticle mean diameter, at 0.2 ~ 2.0mm, comprises following components: acrylic resin, Nucleating Agent, crystallization nucleating agent and fully vulcanized powder rubber.The raw materials melt blending extrusion pelletize including said components is obtained described polypropylene microparticle, the component including disperse medium, foaming agent, dispersant, dispersion intensifier, surfactant and described polypropylene microparticle again joins in hermetic container, heating is to 150 ~ 170 DEG C, the pressure of hermetic container is 1 ~ 6MPa, mixing time is 5min ~ 2h, and blowing obtains polypropylene foaming beads.Described polypropylene microparticle foaming window width, technique is prone to adjust, and gained polypropylene foaming beads and goods rigidity thereof are high, and temperature tolerance is excellent, can be widely applied to auto industry, packaging industry, building trade and aerospace industries.
Description
Technical field
The present invention relates to a kind of polypropylene microparticle and preparation method thereof and the method being prepared polypropylene foaming beads by it and product.
Background technology
Polypropylene foaming beads and goods thereof have as the product size good stability under excellent heat resistance, high temperature, mechanical property and bending modulus are high, impact resistance is good, environment friendly is outstanding, burn time release without poison, the excellent characteristics such as be easily recycled.Therefore, expandable polypropylene resin material is widely used in the fields such as packaging, automobile, building and Aero-Space.
In recent years, market is less for having more high-modulus and proportion, and the demand of the PP foaming product that expansion ratio is higher is growing.Such as, in the traffic transport industries such as automobile, PP foaming product has been widely used for various parts, for instance the shockproof core of the thick stick core of bumper, sunshading board, automobile side, the shockproof core of arrangements for automotive doors, advanced security automotive seat, workbox, boot, handrail, low backing plate, instrumental panel.Electronics in IT industry, liquid crystal display, Plasma Color TV, precise electronic components and parts, precision instrumentation etc. also adopt EPP to make packaging material in a large number.Considering from environmental conservation and energy-conservation angle, the foaming PP goods with higher rigidity and thermostability have good market prospect.Although polystyrene foam product is also widely used in storage and the container for transportation of food and industrial goods at present, yet with it, there is poor shock-resistant and heat resistance, it is not suitable for recycling, therefore, in this field, the demand of the expanded polypropylene goods that density is low, rigidity is high is increasing rapidly.
Compared with common block copolymerization and atactic copolymerized polypropene, HOPP resin has higher high-temperature stability, and intensity is high, has higher modulus, and therefore PP expanded bead prepared therefrom has purposes and prospect of the application widely.But owing to common HOPP is the polymer of a kind of partially crystallizable, molecular weight distribution relative narrower, cause that its softening point and fusing point are closer to, melting range is shorter, when temperature is higher than after fusing point, its melt strength can sharply decline, and causes abscess collapse phenomenon easily occur when foaming.Highly crystalline HOPP abscess phenomenon of caving in is more serious.So normal conditions, can preferred thermostability and the poor atactic copolymerized polypropene of rigidity and block copolymerization polypropylene or PP/PE blend foam, as CN101104716A, CN200410063190.8, CN101679662A, CN101691433A etc. foam with regard to preferred fusing point acrylic resin below 145 DEG C, but this thermostability resulting in its foaming product and rigidity are on the low side.
Summary of the invention
One of the object of the invention there is provided a kind of has high-modulus, heat-resist polypropylene microparticle, and this polypropylene microparticle has the advantages that blowing temperature window is wide.
The preparation method that the two of the purpose of the present invention are to provide a kind of above-mentioned polypropylene microparticle.
The three of the purpose of the present invention are to provide a kind of method adopting above-mentioned polypropylene microparticle to prepare polypropylene foaming beads.Prepared polypropylene foaming beads and goods thereof have the advantages that modulus is high, heat-resist.
The four of the purpose of the present invention are to provide a kind of goods adopting described polypropylene foaming beads.
Polypropylene microparticle of the present invention, its mean diameter, at 0.2 ~ 2.0mm, includes blended following components: acrylic resin, Nucleating Agent, crystallization nucleating agent and fully vulcanized powder rubber.
Described acrylic resin is published polypropylene in prior art, including HOPP COPP or its mixing.
Counting with acrylic resin for 100 parts by weight, polypropylene microparticle of the present invention includes following components: a. HOPP, 100 weight portions；B. Nucleating Agent 0.001 ~ 5 weight portion, it is preferable that 0.01 ~ 3 weight portion；C. crystallization nucleating agent, 0.01 ~ 0.3 weight portion, it is preferable that 0.02 ~ 0.1 weight portion；D. fully vulcanized powder rubber 0.01 ~ 1 weight portion, it is preferable that 0.05 ~ 0.5 weight portion；And conventional general plastic processing additives, such as antioxidant, aid anti-oxidants, lubricant etc..
The polypropylene base resin that polypropylene microparticle of the present invention relates to is preferably HOPP, it is preferable that melt flow rate (MFR) is 0.1 ~ 10g/10min(230 DEG C/2.16Kg) HOPP；Especially preferred melt flow rate (MFR) is 1 ~ 5g/10min(230 DEG C/2.16Kg) HOPP.When melt flow rate (MFR) is less than 0.01g/10min, blend flow is poor, and processing temperature height is unfavorable for foaming.When melt flow rate (MFR) is higher than 10g/10min, polypropylene viscosity is too low is unfavorable for that abscess is grown up.
The HOPP base resin that polypropylene microparticle of the present invention relates to, the high melt strength, propylene of the wide molecular weight distribution that preferred mass polymerization obtains, when it is characterized in that using gel permeation chromatography (GPC) to carry out molecular weight analyse, Mw/Mn(polydispersity coefficient) it is not less than 7.5.The melt strength of HOPP base resin can by squeezing through a diameter 2 millimeter with this device by polymer with 24mm/s speed and length measures for the capillary tube die head of 30 millimeters at 200 DEG C；Then by wire rod, under Constant Acceleration, (acceleration is 20mms-2) stretch, measure percentage elongation simultaneously.The melt strength of HOPP base resin is more preferably at least 20cN, more preferably at 25cN, it is most preferred that at least 30cN；But preferably more than 60cN, more preferably no more than 55cN, it is most preferred that less than 50cN.
Nucleating Agent used in heretofore described polypropylene microparticle is mineral-type Nucleating Agent conventional in prior art, it is possible to the foam cell uniformity of the polypropylene foaming beads prepared is improved, and its addition can be used to regulate the size of bubble.Conventional Nucleating Agent has Pulvis Talci, Borax, Firebrake ZB, aluminium hydroxide, silicon dioxide, magnesium oxide, zinc oxide, calcium carbonate etc., it is preferable that Firebrake ZB and silicon dioxide.Nucleating Agent to acrylic resin abscess be uniformly distributed and steady growth plays an important role, the size of abscess can be controlled by regulating its consumption.With acrylic resin consumption for 100 parts by weight, the consumption of Nucleating Agent is 0.001 ~ 5 part, it is preferred to 0.01 ~ 3 part.
When acrylic resin adds Nucleating Agent, it is possible to be directly mixed with in PP resin, it is also possible to carry out blended with PP resin again after making masterbatch.
The crystallization nucleating agent used in polypropylene microparticle of the present invention, thus it is possible to vary the degree of crystallinity of acrylic resin and crystal habit, thus improving its rigidity and thermostability.In body series, crystallization nucleating agent can also effectively widen the blowing temperature window of PP compositions, makes processing technique be more prone to control.Described crystallization nucleating agent is organophosphorus compounds nucleator, i.e. (replacement) aryl phosphate ester salt.Preferably two (4-tert-butyl-phenyl) sodium ascorbyl phosphate (NA-10), di-2-ethylhexylphosphine oxide (2,4-di-tert-butyl-phenyl) phosphoric acid ester sodium (NA-11), di-2-ethylhexylphosphine oxide (2,4-di-tert-butyl-phenyl) phosphate ester hydroxyl aluminium salt (NA-21).With acrylic resin consumption for 100 parts by weight, crystallization nucleating agent consumption is 0.01 ~ 0.3 part, it is preferred to 0.02 ~ 0.1 part.Described crystallization nucleating agent consumption too much can cause particle aggregation, and nucleation reduces, and also can increase the cost of material；Consumption is very few it cannot be guaranteed that compositions has the heterogeneous nucleation of abundance, reduces rigidity and the thermostability of material, nor is beneficial to the scope improving blowing temperature window.
In polypropylene microparticle of the present invention, selecting fully vulcanized powder rubber is crystallization nucleation auxiliary agent, and organic phosphate nucleating agent plays synergism and peptizaiton.The mean diameter of described fully vulcanized powder rubber is 50 ~ 200nm, it is preferred to 80 ~ 150nm；Gel content is 60% weight or higher, it is preferred to 80% weight or higher.This kind of fully vulcanized powder rubber is preferably the rubber particles of equal phase structure.Described fully vulcanized powder rubber is entirely vulcanize at least one in butylbenzene powdered rubber and full sulfuration Carboxy powdered rubber, it is preferred to entirely vulcanize butylbenzene powdered rubber.With acrylic resin consumption for 100 parts by weight, fully vulcanized powder rubber consumption is 0.01 ~ 1 part, it is preferred to 0.05-0.5 part.Described fully vulcanized powder rubber consumption too much can reduce rigidity and the heat resistance of acrylic resin, and consumption crosses the dispersibility that can reduce organic phosphate nucleating agent at least, does not reach good nucleating effect.
Heretofore described fully vulcanized powder rubber is the fully vulcanized powder rubber disclosed in Chinese patent application CN1402752A.This kind of fully vulcanized powder rubber refers to that gel content reaches 60wt% or higher, more preferably 75wt% or higher, after drying without with interleaving agent and free flowable rubber micropowder.The particle diameter of this fully vulcanized powder rubber is 20nm ~ 2000nm.Each microgranule in this fully vulcanized powder rubber is homogeneous, and namely single microgranule is all homogenizing on composition.Layering, point equal not homogeneous phenomenon is not found in microgranule under the observation of existing microtechnique.This powdered rubber is by fixing corresponding rubber latex cross-linking radiation rubber particles particle diameter.The product that current fully vulcanized powder rubber has been produced by Sinopec Beijing Research Institute of Chemical Industry is commercially available.
Polypropylene microparticle of the present invention can also include the processing aid that polypropylene is conventional, such as antioxidant, lubricant etc..Wherein antioxidant such as primary antioxidants 1010,1076,1330 etc., auxiliary antioxidant is anti-oxidant DLTP, DSTP etc. such as；Lubricant has calcium stearate, zinc stearate, stearic acid, EBS etc..The consumption of these conventional processing aids is conventional amount used, or the requirement according to practical situation suitably adjusts.
The preparation method of polypropylene microparticle of the present invention, comprises the following steps:
HOPP, Nucleating Agent, crystallization nucleating agent, fully vulcanized powder rubber and other auxiliary agents will be included after interior component is by formula ratio mix homogeneously, extruded machine melt blending extruding pelletization, make polypropylene microparticle.The blending equipment of mixing of materials can adopt mixing equipment used in prior art, such as blender, kneader etc.；Material melts blending equipment is the general blending equipment in rubber and plastic processing industry, it is possible to be double screw extruder, single screw extrusion machine and multi-screw extruder.Material melts blending temperature is the blending temperature that the processing of usual polypropylene is used, can determine according to polypropylene fusion temperature, it should not only can ensure that polypropylene matrix plastics are completely melted but also will not make to select in its scope decomposed, be typically in 160 DEG C ~ 240 DEG C.Its pelletize mode mainly has two kinds: one is underwater pelletization (UWC method), in UWC method, acrylic resin under molten condition flows directly out in the water of 30 ~ 95 DEG C from the die head being provided with multiple micropore, adopting rotary cutter to carry out cutting resin in water, the size of resin particle and the diameter of nib, the quantity of nib, the pressure of die head, the quantity of cutter head and rotary speed thereof etc. are relevant；Another kind is check rod patterning method, and the method arranges micropore on die template, and melt polypropylene is fed in tank after extruding from micropore cooling curing, then cuts into microparticle with cutting machine.The diameter of microparticle is between 0.2mm ~ 2.0mm, it is preferable that 0.4 ~ 1.2mm.
Present invention also offers a kind of method adopting polypropylene microparticle to prepare polypropylene foaming beads, usual step that the method can adopt in prior art in the preparation technology of polypropylene foaming beads and parameter, specifically include following steps:
The component including disperse medium, foaming agent, dispersant, dispersion intensifier, surfactant and described polypropylene microparticle is joined in hermetic container, heating is to 150 ~ 170 DEG C, the pressure of hermetic container is 1 ~ 6MPa, mixing time is 5min ~ 2h, then rapid blowing, obtains polypropylene foaming beads.
Described disperse medium, foaming agent, dispersant, dispersion intensifier, surfactant etc., be also auxiliary agent conventional in the preparation technology of polypropylene foaming beads in prior art.Its consumption is also usual consumption.Specifically:
Described disperse medium at least one in water, ethylene glycol, glycerol, formaldehyde, ethanol.Preferred water does disperse medium, more preferably deionized water.For the polypropylene microparticle of every 100 weight portions, the consumption that makes of this disperse medium is generally 100 ~ 2000 parts, preferential 200 ~ 500 weight portions.
Described foaming agent is selected from physical blowing agent, it is possible to be a kind of organic physical blowing agent or a kind of inorganic physical blowing agent.The example of this organic physical blowing agents includes aliphatic alkane such as propane, butane, pentane, hexane and heptane, alicyclic hydro carbons such as Tetramethylene. and hexamethylene, and halogenated hydrocarbon such as chlorofluoromethane, fluoroform, 1,2-Difluoroethane, 1,2,2,2-tetrafluoroethane, methyl chloride, ethyl chloride and dichloromethane.The example of inorganic physical blowing agent includes air, nitrogen, carbon dioxide, oxygen, argon and water.These organic and inorganic foaming agents can be used alone, it is also possible to the mixing as two or more uses.From the stability (homogeneity) of expanded polypropylene beads apparent density, low cost and environmental protection angularly, it is preferred to use carbon dioxide, air or nitrogen.Under blowing temperature, these foaming agent are all gaseous states, and the pressure of reactor is exactly that foaming agent provides.Foaming agent consumption and reactor pressure correlation, can control the addition of foaming agent by the Stress control of reactor.
Described dispersant is the dispersant of organic or inorganic solid, and granule is tiny, can be used to prevent microparticle surfaces in foaming process from mutually bonding.For consideration easy and simple to handle, it is preferred to inorganic powder.Its kind includes natural or that synthesize clay mineral (such as Kaolin, Muscovitum, pyrope and clay), Alumina, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate and ferrum oxide.For the acrylic resin microparticle of 100 weight portions, the consumption that makes of this dispersant is generally 0.001 ~ 6 weight portion, it is preferable that 0.001 ~ 5 weight portion.
Described dispersion intensifier is when 40 DEG C, dissolubility >=1mg, and can provide bivalence or trivalent, anion or cationic inorganic compound.The Main Function of dispersion intensifier is the dispersion efficiency improving dispersant, namely retains its function preventing PP microparticle melt to be bonded to each other while reducing dispersant quantity.The example of this dispersion intensifier includes magnesium chloride, magnesium nitrate, magnesium sulfate, aluminum chloride, aluminum nitrate, aluminum sulfate, iron chloride, iron sulfate and ferric nitrate.For the polypropylene microparticle of every 100 weight portions, the consumption that makes of this dispersion intensifier is generally 0 ~ 2 weight portion, it is preferable that 0.001 ~ 1 weight portion.
Described surfactant is at least one in anionic surfactant, nonionic surfactant.Polypropylene microparticle is mainly played infiltration left and right by described surfactant, is conducive to PP microparticle dispersion effect in disperse medium.Wherein anionic surfactant includes sulfonate, such as the sulfoalkyl amide (IgeponT is serial) etc. of sodium n-alkylbenzenesulfonate (LAS), α-sodium olefin sulfonate (AOS), sodium alkyl sulfonate (SAS), sulphosuccinates, lignosulfonates, alpha-sulfo fatty acid methyl ester (list) sodium salt (MES), the sulfoalkyl ester (IgeponA series) of fatty acid and fatty acid；Carboxylic acid type, such as soap etc.；Sulfuric ester salt form, such as fatty alcohol sulphuric acid (ester) salt (FAS), polyoxyethylenated alcohol sodium sulfate (AES) etc..Its consumption is the 0.01% ~ 0.5% of dispersant, it is preferred to 0.05% ~ 0.2%.Wherein nonionic surfactant includes polyethenoxy ether class, such as fatty alcohol-polyoxyethylene ether (AEO), polyoxyethylene carboxylate, alkylphenol polyoxyethylene (APEO), polyoxyethylate amide, polyoxyethylene fatty amine, tween (main chemical compositions is polyoxyethylene sorbitan mono fatty acid ester) etc.；Polyalcohols, such as ethylene glycol fatty acid, mono fatty acid glyceride (monoglyceride), pentaerythritol fatty ester, sorbitan fatty acid ester, sucrose fatty acid ester etc.；Polyethers, i.e. oxirane and propylene oxide block copolymer；Alkanolamide class, such as fatty diglycollic amide, fatty monoethanol amide, amine-oxides and alkyl polyglycoside (APG) etc..Its consumption is the 0.01% ~ 0.5% of dispersant, it is preferred to 0.05% ~ 0.2%.
Prepared polypropylene foaming beads stands 48h after drying, adopts drainage to measure its apparent density, and calculates its expansion ratio accordingly.
Polypropylene microparticle of the present invention has the following characteristics that
(1) the homopolymerization high melt strength, propylene being distributed with the wide molecular weight of polymerisation in bulk is for raw material, makes polypropylene microparticle have foaming window width, and technique is prone to the advantage adjusted, and raw material sources are extensive, it is possible to cost is greatly lowered.
(2) due in fully vulcanized powder rubber rubber phase and nucleator component in PP matrix dispersed, fully vulcanized powder rubber and organophosphorus ester nucleator can produce certain cooperative effect, acrylic resin and foaming product thereof can be made to have good rigidity, thermostability and good processing characteristics, decrease nucleator consumption, reduce cost.
The polypropylene foaming beads utilizing polypropylene microparticle of the present invention to prepare, has the advantages that heat resisting temperature is high.EPP goods prepared by this polypropylene foaming beads are adopted to have rigidity height, the advantage that temperature tolerance is excellent, can be applicable to the parts in auto industry, packaging industry, building trade and aerospace industries, the intensity of PP foam material and heatproof being had higher requirements.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is specifically described; be necessary it is pointed out here that be that following example are served only for further illustrating the present invention; it is not intended that limiting the scope of the invention, some nonessential improvement that the present invention is made according to present invention by the person skilled in the art in this field and adjust and still belong to protection scope of the present invention.
The raw material that the present invention relates to includes:
High melt strength, propylene: China petroleum Chemicals Co., Ltd. Town Hai Lian Hua branched Corporation, trade mark HMS20Z.The high fondant-strength HOPP of wide molecular weight distribution prepared by mass polymerization, Mw/Mn=11, melt strength 45cN, melting means is 2.2 ± 0.3g/10min (230 DEG C, 2.16Kg).(please consider whether to need to describe in detail)
Common HOPP: China petroleum Chemicals Co., Ltd. Town Hai Lian Hua branched Corporation, trade mark T30S；Mw/Mn=5, melt strength 12cN, melting means is 3.0 ± 0.3g/10min (230 DEG C, 2.16Kg).
NA-11: crystallization nucleating agent, di-2-ethylhexylphosphine oxide (2,4-di-tert-butyl-phenyl) phosphoric acid ester sodium, electricity Xu Hua company of Japan；
Full sodium sulfide meter level butylbenzene powdered rubber: Sinopec Beijing Chemical Research Institute produces, and the trade mark is VP101, mean diameter 100nm, gel content 90%)；
Full sodium sulfide meter level Carboxy powdered rubber: Sinopec Beijing Chemical Research Institute produces, and the trade mark is VP201, mean diameter 80nm, gel content 90%)；
Firebrake ZB: Nucleating Agent, Tianjin recovery fine chemistry industry institute；
Dodecylbenzene sodium sulfonate (SDBS): Tianjin recovery fine chemistry industry institute；
Kaolin: ACROSOrganics company；
Aluminum sulfate: Tianjin recovery development in science and technology company limited.
Deionized water: Sinopec Beijing Chemical Research Institute produces.
Carbon dioxide: Long Hui capital, Beijing gas company limited
Method of testing of the present invention includes:
1, heat distortion temperature: test according to GB/T1634；
2, bending modulus: test according to GB/T9341；
3, expansion ratio: adopt Satorius company of Germany to produce the density tester CPA225D being accompanied with density adnexa YDK01 and carry out density measurement, its concrete grammar is as follows: uses the density adnexa of Satorius balance, utilizes drainage to obtain the density of polypropylene base resin and polypropylene foamed sheet.The expansion ratio formula of the PP foam material obtained calculates: b=ρ 1/ ρ 2, and wherein, b is expansion ratio, and ρ 1 is the density of polypropylene base resin, and ρ 2 is the apparent density of expanded material.
Embodiment 1 ~ 12 formula and performance data are listed in table 1, and embodiment 13 ~ 20 formula and performance data are listed in table 2, and comparative example 1 ~ 12 formula and performance data are listed in table 3.
Embodiment 1 ~ 23:
By the crystallization nucleating agent NA-11 of 100 weight portion high melt strength, propylene HMS20Z and formula ratio, full sodium sulfide nanoscale powder butadiene-styrene rubber VP-101, full sodium sulfide nanoscale powder carboxylic styrene-butadiene rubber VP-201, Firebrake ZB, 0.1 weight portion antioxidant 1010 (BASF AG), 0.1 weight portion irgasfos 168 (BASF AG) mix homogeneously in homogenizer；Compound produces in CTE-35 double screw extruder in grand (Nanjing) Machinery Co., Ltd. again of section and melt extrudes, melt extrude temperature range and be 200-260 DEG C, adopting BKG company to produce Labline100 type underwater pellet cutting system and carry out the preparation of microparticle, the mean diameter of microparticle controls between 0.6 ~ 1.2mm.
Being mixed by above-mentioned polypropylene microparticle 100 weight portion, deionized water 300 weight portion, the surfactant SDBS of formula ratio, dispersant Kaolin and the dispersion intensifier aluminum sulfate etc. prepared is positioned in closed reactor, pass into carbon dioxide, heat up heating to design temperature, the time 30min that continuous stirring sets when keeping test pressure, then quickly it is discharged in surge tank, carbon dioxide or nitrogen can be passed in reactor to keep the pressure in reactor during blowing, obtain polypropylene foaming beads.This polypropylene foaming beads is scrubbed, dried stands more than 48h in an atmosphere, then carries out the measurement of expansion ratio.
Comparative example 1 ~ 5:
Except being not added with butylbenzene powdered rubber and/or crystallization nucleating agent, other conditions are all identical with previous embodiment.Wherein comparative example 1 is not added with powdered rubber and nucleant agent N A-11；Used by comparative example 2 and embodiment 1 ~ 5, crystallization nucleating agent NA-11 composition is identical, but without powdered rubber；Used by comparative example 3 and embodiment 6 ~ 11, crystallization nucleating agent NA-11 composition is identical, but without powdered rubber；Used by comparative example 4 and embodiment 12 ~ 16, crystallization nucleating agent NA-11 composition is identical, but without powdered rubber；Comparative example 5 adds NA-11 in 0.1 part of crystallization nucleating agent, without powdered rubber.Concrete formula is referring to table 3, and wherein each component is all with parts by weight.Relevant test result is as shown in table 3.
Contrasted from the results of property of comparative example 1 ~ 5 with corresponding embodiment, high melt strength, propylene HMS20Z adds appropriate powdered rubber and crystallization nucleating agent can make the rigidity of acrylic resin and heat distortion temperature be improved, powdered rubber can be effectively improved crystallization nucleating agent dispersibility in HMS20Z, improve crystallization nucleating agent efficiency, reduce the consumption of organic phosphate crystallization nucleating agent, thus reducing the cost of material.
Comparative example 6 ~ 8:
Except being changed into T30S except the acrylic resin trade mark by HMS20Z, other conditions are identical with previous embodiment.Except resin grade is substituted by T30S, wherein comparative example 6 is identical with embodiment 4, and comparative example 7 is identical with embodiment 7, and comparative example 8 is identical with embodiment 14.Concrete formula is referring to table 2, and wherein each component is all with parts by weight.Relevant test result is as shown in table 2.
By comparative example 6 and embodiment 4, comparative example 7 and embodiment 11, contrast between comparative example 8 and embodiment 14 is it can be seen that owing to high melt strength, propylene HMS20Z has higher melt intensity relative to common HOPP T30S, it is possible to obtain higher expansion ratio.
Comparative example 9 ~ 12:
Comparative example 9, comparative example 11 are distinctive in that with embodiment 17, and comparative example 9 is not added with NA-11 crystallization nucleating agent and powdered rubber, comparative example 11 are not added with NA-11 crystallization nucleating agent；Comparative example 10, comparative example 12 are distinctive in that with embodiment 18, and comparative example 10 is not added with NA-11 crystallization nucleating agent and powdered rubber, comparative example 12 are not added with NA-11 crystallization nucleating agent.
By comparative example 9, comparative example 11 and embodiment 17, contrast between comparative example 10, comparative example 12 and embodiment 18 can be seen that, the foaming window being not added with compositions during nucleator is narrower, when temperature is higher (more than 168 DEG C), the abscess collapse phenomenon of expanded bead is serious, and the expansion ratio of the EPP beadlet prepared is low.
Claims (21)
1. a polypropylene microparticle, its mean diameter, at 0.2～2.0mm, includes blended following components: acrylic resin, Nucleating Agent, crystallization nucleating agent and fully vulcanized powder rubber；
Described Nucleating Agent is mineral-type Nucleating Agent；Described crystallization nucleating agent is organophosphorus compounds nucleator；Described fully vulcanized powder rubber is entirely vulcanize at least one in butylbenzene powdered rubber and full sulfuration Carboxy powdered rubber, and its mean diameter is 50～200nm, and gel content is 60%wt or higher；
Wherein, count with acrylic resin for 100 parts by weight, Nucleating Agent 0.001～5 parts by weight, crystallization nucleating agent 0.01～0.3 parts by weight, fully vulcanized powder rubber 0.01～1 parts by weight.
2. polypropylene microparticle as claimed in claim 1, it is characterised in that:
Described polypropylene microparticle, its mean diameter is at 0.4～1.2mm.
3. polypropylene microparticle as claimed in claim 1, it is characterised in that:
Counting with polypropylene for 100 parts by weight, Nucleating Agent is 0.01～3 parts by weight, and crystallization nucleating agent is 0.02～0.1 parts by weight, and fully vulcanized powder rubber is 0.05～0.5 parts by weight.
4. polypropylene microparticle as claimed in claim 1, it is characterised in that:
Described polypropylene is HOPP, is 230 DEG C in test temperature, and load is melt index during 2.16Kg is 0.1～10.0g/10min.
5. polypropylene microparticle as claimed in claim 4, it is characterised in that:
Described HOPP is 230 DEG C in test temperature, and load is melt index during 2.16Kg is 1.0～5.0g/10min.
6. polypropylene microparticle as claimed in claim 4, it is characterised in that:
Described HOPP is the high fondant-strength HOPP of wide molecular weight distribution prepared by mass polymerization, and its Mw/Mn is not less than 7.5, and its melt strength is 20～60cN.
7. polypropylene microparticle as claimed in claim 6, it is characterised in that:
The melt strength of described high fondant-strength HOPP is 25～50cN.
8. polypropylene microparticle as claimed in claim 1, it is characterised in that:
The Nucleating Agent in described polypropylene microparticle at least one in Pulvis Talci, Borax, Firebrake ZB, aluminium hydroxide, silicon dioxide, magnesium oxide, zinc oxide, calcium carbonate.
9. polypropylene microparticle as claimed in claim 1, it is characterised in that:
Crystallization nucleating agent in described polypropylene microparticle is two (4-tert-butyl-phenyl) sodium ascorbyl phosphate, di-2-ethylhexylphosphine oxide (2,4-di-tert-butyl-phenyl) phosphoric acid ester sodium, di-2-ethylhexylphosphine oxide (2,4-di-tert-butyl-phenyl) phosphate ester hydroxyl aluminium salt at least one.
10. polypropylene microparticle as claimed in claim 1, it is characterised in that:
The mean diameter of described fully vulcanized powder rubber is 80～150nm.
11. polypropylene microparticle as claimed in claim 1, it is characterised in that:
The gel content of described fully vulcanized powder rubber is 80%wt or higher.
12. the method for making of the polypropylene microparticle as according to any one of claim 1～11 is:
By including described acrylic resin, Nucleating Agent, crystallization nucleating agent, fully vulcanized powder rubber after interior component is by described amount mix homogeneously, through melt blending extruding pelletization, make described polypropylene microparticle.
13. the method for making of polypropylene microparticle as claimed in claim 12, it is characterised in that:
Described pelletize is to adopt underwater pelletization or adopt check rod patterning method that the melt polypropylene that melt blending is extruded is cut into the microparticle in described particle diameter, thus obtaining described polypropylene microparticle.
14. the method that the polypropylene microparticle that employing is as according to any one of claim 1～11 prepares polypropylene foaming beads is:
The component including disperse medium, foaming agent, dispersant, dispersion intensifier, surfactant and described polypropylene microparticle is joined in hermetic container, heating is to 150～170 DEG C, the pressure of hermetic container is 1～6MPa, mixing time is 5min～2h, then rapid blowing, obtains polypropylene foaming beads.
15. the method that polypropylene microparticle as claimed in claim 14 prepares polypropylene foaming beads, it is characterized by:
The above disperse medium at least one in water, ethylene glycol, glycerol, formaldehyde, ethanol；
The above foaming agent is selected from physical blowing agent；
The above dispersant is the dispersant of organic or inorganic solid；
The above dispersion intensifier is when 40 DEG C, dissolubility >=1mg, and can provide bivalence or trivalent, anion or cationic inorganic compound；
The above surfactant is at least one in anionic surfactant, nonionic surfactant；
Count with polypropylene microparticle for 100 parts by weight, the above disperse medium is 100～2000 parts, described dispersant is 0.001～6 weight portion, and described dispersant reinforcing agent is 0～2 weight portion, and described surfactant is the 0.01%～0.5% of described dispersant weight.
16. the method that polypropylene microparticle as claimed in claim 15 prepares polypropylene foaming beads, it is characterized by:
Counting with polypropylene microparticle for 100 parts by weight, the above disperse medium is 200～500 weight portions.
17. the method that polypropylene microparticle as claimed in claim 15 prepares polypropylene foaming beads, it is characterized by:
Counting with polypropylene microparticle for 100 parts by weight, described dispersant is 0.001～5 weight portion.
18. the method that polypropylene microparticle as claimed in claim 15 prepares polypropylene foaming beads, it is characterized by:
Counting with polypropylene microparticle for 100 parts by weight, described dispersant reinforcing agent is 0.001～1 weight portion.
19. the method that polypropylene microparticle as claimed in claim 15 prepares polypropylene foaming beads, it is characterized by:
Described surfactant is the 0.05%～0.2% of described dispersant weight.
20. the method that the polypropylene microparticle according to any one in claim 15-19 prepares polypropylene foaming beads, it is characterised in that:
The above foaming agent selected from propane, butane, pentane, hexane, heptane, Tetramethylene., hexamethylene, chlorofluoromethane, fluoroform, 1,2-Difluoroethane, 1,2, at least one in 2,2-tetrafluoroethane, methyl chloride, ethyl chloride, dichloromethane, air, nitrogen, carbon dioxide, oxygen, argon and water；
The above dispersant at least one in Alumina, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate and ferrum oxide, naturally occurring or synthetic clay mineral；
The above dispersion intensifier at least one in magnesium chloride, magnesium nitrate, magnesium sulfate, aluminum chloride, aluminum nitrate, aluminum sulfate, iron chloride, iron sulfate and ferric nitrate；
The above anionic surfactant at least one in sodium n-alkylbenzenesulfonate, α-sodium olefin sulfonate, sodium alkyl sulfonate, sulphosuccinates, lignosulfonates, alpha-sulfo fatty acid methyl ester list sodium salt, the sulfoalkyl ester of fatty acid, the sulfoalkyl amide of fatty acid, soap, fatty alcohol sulfate or fat sulphate, polyoxyethylenated alcohol sodium sulfate；Nonionic surfactant at least one in fatty alcohol-polyoxyethylene ether, polyoxyethylene carboxylate, alkylphenol polyoxyethylene, polyoxyethylate amide, polyoxyethylene fatty amine, tween, ethylene glycol fatty acid, the mono fatty acid glyceride of monoglyceride, pentaerythritol fatty ester, sorbitan fatty acid ester, sucrose fatty acid ester, oxirane and propylene oxide block copolymer, fatty diglycollic amide, fatty monoethanol amide, amine oxide, alkyl polyglycoside.
21. the polypropylene microparticle that employing is as described in any one of claim 14～20 prepares the product of the method gained of polypropylene foaming beads.
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| WO2021112623A1 (en) * | 2019-12-04 | 2021-06-10 | 주식회사 엘지화학 | Polypropylene resin, polypropylene fiber and method for preparing same |
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