CN103073868A - Biodegradable melt-blown non-woven fabric sliced sheet and preparation method thereof - Google Patents
Biodegradable melt-blown non-woven fabric sliced sheet and preparation method thereof Download PDFInfo
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- CN103073868A CN103073868A CN2013100128848A CN201310012884A CN103073868A CN 103073868 A CN103073868 A CN 103073868A CN 2013100128848 A CN2013100128848 A CN 2013100128848A CN 201310012884 A CN201310012884 A CN 201310012884A CN 103073868 A CN103073868 A CN 103073868A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention discloses a biodegradable melt-blown non-woven fabric sliced sheet and a preparation method thereof. The biodegradable melt-blown non-woven fabric sliced sheet comprises the following components in part by mass: 50-90 parts of polypropylene carbonate, 10-50 parts of polypropylene melt-blown non-woven fabric sliced sheets, 0-40 parts of nano-particles, 0-10 parts of bulking agent, 0-8 parts of end-capping reagent, 0-0.1 part of initiating agent, 0-2 parts of heat-resisting stabilizing agent, 0-2 parts of slipping agent, 0-2 parts of biodegradation accelerant and 0-1 part of photolysis agent; and the preparation method comprises the following steps: drying the components for 6-12 h at the temperature of 45-55 DEG C; performing melt blending in proportion in mixing equipment, wherein the blending temperature is 100-210 DEG C, the blending time is 3-8 min, and the rotating speed is 15-50 r/min; and then performing extrusion and granulation on the blend through a single-screw or double-screw extruder, wherein the temperature of the extruder is 100-210 DEG C, and the rotating speed is 15-50 r/min. According to the biodegradable melt-blown non-woven fabric sliced sheet provided by the invention, the tensile strength can reach 25.86 MPa to the maximum, the melt flow rate is 800-3000 g/10min, the glass-transition temperature Tg can reach 28.37 DEG C to the maximum, and the thermal decomposition temperature T(-5%) can reach 260 DEG C to the maximum.
Description
Technical field
The present invention relates to a kind of melt spraying non-woven fabrics section and preparation method thereof, particularly a kind of biodegradable melt spraying non-woven fabrics section and preparation method thereof belongs to non-woven fabrics manufacturing technology field.
Background technology
Non-woven fabrics claims again tNonwovens, is to be made of orientation or random fiber, has protection against the tide, ventilative, pliable and tough, light weight, not combustion-supporting, easy decomposition, nontoxic, nonirritant, rich color, lower-price characteristic.The production technology of non-woven fabrics mainly contains spun-bond process, meltblown, pulp air-lay process method, pin (water) acupuncture manipulation, chemical adhesion method and heat viscosity method etc.Wherein meltblown is a kind of novel and rising new technology; have the advantages such as technique advanced person, flow process is short, with low cost, raw material is easy to get, development is rapid, particularly in recent years; along with the develop rapidly of industry and to the reinforcement of environment protection, the market of melt spraying non-woven fabrics is increasing.Meltblown be rely at a high speed, high temperature gas flow winding-up polymer melt stretches rapidly it and prepares a kind of method of ultra-fine fibre.After polymer chips becomes molten state by the extrusion machine heating and pressurizing, arrive the orifice of shower nozzle front end through melt flow road, stretching through high speed, the high temperature gas flow of two bursts of convergences after the extruding makes it super-refinement again.The fiber cooling curing of super-refinement also is deposited on the collection lace curtaining device, forms the superfine melt-blowing nonwoven of fiber number.The Fibre diameter that meltblown is produced is at 2 ~ 5 μ m, even can produce the non-woven that average fibre diameter is 1 μ m.Because the fiber that melt blown technology is produced is very thin, fusion spray cloth has very large specific surface area simultaneously, and the space is little and voidage is large, is difficult to possess therefore the application characteristics such as its filterableness, shielding, heat insulating ability and oil absorbency are the non-woven fabrics of other independent explained hereafter.So melt spraying non-woven fabrics is widely used in the fields such as medical and industrial face mask, heat insulating material formed, filtering material, medical and health, oil absorption material, cleaning wiping cloth, battery separator and sound-proof material.
Polypropylene is the main raw material of producing non-woven fabrics, accounts for more than 60% of all non-woven fabrics raw materials.But polypropylene belongs to linear saturated hydrocarbon, if its discarded rear burning will produce obnoxious flavour, is difficult to occur microbiological deterioration if bury.Research is found, after polypropylene fabric is buried in underground 450d, is not observed the phenomenon of strength degradation; Under the natural condition through 12 months the intensity that still has more than 40% of tanning by the sun.As seen the photoaging of plain polypropylene degraded neither be processed the effective measure of polypropylene waste gurry.Therefore, the waste of namely abandoning the polypropylene non-woven fabric material of product as usefulness such as environment-friendly shopping bag and disposable hygienic and medical treatment has in a large number brought huge pressure to environment protection.For this reason, the research of the degradable of polypropylene melt-blown nonwoven cloth material waste has become one of focus of present research.
Aliphatic polycarbonate by carbonic acid gas and epoxy compounds copolymerization has biodegradable, is the environmental protection polymer that a class can be degradable, is commonly called as carbon dioxide plastic.Poly (propylene carbonate) is carbonic acid gas (CO
2) and the alternating copolymer of propylene oxide (PO), wherein CO
2Content accounts for 31%～50%, can greatly reduce the consumption to oil.Poly (propylene carbonate) has the good transparency, degradability, high barrier, bio-compatibility, can be applicable to injection moulding and extruded product, fibre product and blow-molded article by modifying plastics processing, can substitute many non-degradable products that use in the fields such as medicine, food and agricultural.Country's plastic products quality Supervision Test Center adopts the controlled composting experimental technique, and the poly (propylene carbonate) foam material is carried out the biological degradation experiment.Standard GB/T/T19277-2003 is quoted in experiment, under the aerobic composting condition of simulation, determine final aerobic biodegradability ability by measuring its discharging amount of carbon dioxide, wherein compost comes compost self stabilization, that become thoroughly decomposed, reference material is Mierocrystalline cellulose, experimental temperature is 58 ℃, and the result shows that 45 days biological rate of decomposition are that 28.2%, 90 day biological degradation rate is 49.9%.
So by melt blending can balanced each polymeric constituent performance, learn from other's strong points to offset one's weaknesses, eliminate the weakness on each single polymers component property, obtain the comparatively desirable polymer materials of over-all properties.Medium EVOH and the poly (propylene carbonate) used of the Meng Yue of Zhongshan University is 170 ℃ of lower simple blend.Find the adding of EVOH, clearly improved the temperature (T of the weightlessness 5% of poly (propylene carbonate)
-5%) and T
MaxPang is only bought and to be waited with polystyrene and poly (propylene carbonate) blend, when polystyrene content reaches after 30%, and all sharply increases along with the increase of PS content of tensile strength and Young's modulus; Less than 50% the time, material is still keeping larger elongation at break in polystyrene content.The introducing of polystyrene is so that the T of PPC
Max10 ℃～15 ℃ have been improved, the T of system
-5%Improve 80 ℃ nearly, thereby improved the thermostability of matrix material.Pang Hao etc. have studied the pyrolysis of poly (propylene carbonate)/styrene-butadiene rubber(SBR) with styrene-butadiene rubber(SBR) and poly (propylene carbonate) blend.The thermal degradation activation energy data verification poly (propylene carbonate) and styrene-butadiene rubber(SBR) form the interface interpenetrating(polymer)networks, network interpenetrating part thermal degradation activation energy obviously raises.Up to now, the research about poly (propylene carbonate) and the section of polypropene blended preparation degradable melt spraying non-woven fabrics at home and abroad there is no report.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of biodegradable melt spraying non-woven fabrics section and preparation method thereof.The present invention is with poly (propylene carbonate) and polypropylene melt blown non-woven fabric section melt blending, prepare the biodegradable melt spraying non-woven fabrics section with premium properties, to solve the problem of the aspects such as product molding processibility, heat-resistant stability, mechanical property, melt flow rate (MFR), consistency, degradability.
For achieving the above object, the invention provides a kind of biodegradable melt spraying non-woven fabrics section, described melt spraying non-woven fabrics section is made by the material combination of following mass parts: poly (propylene carbonate) 50-90 part; Polypropylene melt blown non-woven fabric section 10-50 part; 0 ~ 40 part of nanoparticle; 0 ~ 10 part of expanding material; End-capping reagent 0-8 part; Initiator 0-0.1 part; 0 ~ 2 part of heat-resisting stabilizing agent; 0 ~ 2 part of slipping agent; 0 ~ 2 part of biodegradation promotor; 0 ~ 1 part of photolysis agent is so that the performance of melt spraying non-woven fabrics provided by the present invention section is better.
Further, wherein said melt spraying non-woven fabrics section is made by the material combination of following mass parts: 80 parts of poly (propylene carbonate)s; 20 parts of polypropylene melt blown non-woven fabric sections; 25 parts of nanoparticles; 2 parts of expanding materials; 1 part of end-capping reagent; 0.01 part of initiator; 1 part of heat-resisting stabilizing agent; 1 part of slipping agent; 0.5 part of biodegradation promotor; 0.2 part of photolysis agent.
Further, the number-average molecular weight of wherein said poly (propylene carbonate) is 40000-140000Da, second-order transition temperature T
gBe 19-25 ℃, tensile strength is 3-8MPa.
Further, the number-average molecular weight of wherein said polypropylene melt blown non-woven fabric section is 30000-60000Da, melting index〉800g/10min (230 ℃ of experimental temperatures, nominal load 2160g).
Further, wherein said nanoparticle is at least a in the following substances: nano-calcium carbonate, nano barium sulfate or nano imvite etc.
Further, wherein said expanding material is at least a in the following substances: maleic anhydride inoculated polypropylene PP-g-MAH, glycidyl methacrylate-styrene-grafted polypropylene PP-g-(GMA-co-St), maleic anhydride-styrene graft polypropylene PP-g-(MAH-co-St) or styrene-grafted polypropylene PP-g-St etc.
Further, wherein said end-capping reagent is at least a in the following substances: maleic anhydride, methyl alcohol, phthalic anhydride, naphthalene acid anhydride or Di-n-Butyl Amine.
Further, wherein said initiator is at least a in the following substances: benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, di-t-butyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate or di-cyclohexylperoxy dicarbonate.
Further, wherein said heat-resisting stabilizing agent is at least a in the following substances: polynite, nano silicon, kaolin or zinc oxide.
Further, wherein said slipping agent is at least a in the following substances: erucic acid phthalein amine, stearic phthalein amine, Zinic stearas or oleic acid phthalein amine.
Further, wherein said biodegradation promotor is at least a in the following substances: oxalic acid or citric acid etc.
Further, wherein said photolysis agent is at least a in the following substances: st-yrax monoalky lether, thioxanthone, benzophenone, benzoin dimethylether or 1-hydroxy-cyclohexyl phenyl ketone etc.
The present invention also provides a kind of preparation method of above-mentioned biodegradable melt spraying non-woven fabrics section, its process is as follows: with above-mentioned each component under 45-55 ℃ condition dry 6-12h (because poly (propylene carbonate) easily absorbs water, in drying process for preventing that it from absorbing water again, can put into some potassium hydroxide and make water-retaining agent), dried each component is mixed 0.5-3min according to the above ratio in high-speed mixer, then melt blending makes the blend masterbatch in mixing facilities, blending temperature is 100-210 ℃, the blend time is 3-8min, and rotating speed is 15-50r/min; Again the blend masterbatch is pulverized 0.5-3min in high-speed mixer afterwards, pulverizing is passed through single screw rod or twin screw extruder extruding pelletization after making powder, and extruder temperature 100-210 ℃, rotating speed is 15-50r/min, obtains described melt spraying non-woven fabrics section.
Further, wherein said high-speed mixer is high speed disintegrator; Described mixing facilities is Banbury mixer (can only finish the banburying blend), single screw extrusion machine or twin screw extruder (can finish simultaneously banburying and extrude).
Further, wherein when described melt blending carries out in twin screw extruder, the process of described melt blending is as follows: with the hopper blanking of mixed described each component from twin screw extruder, pellet through one, two, three district's conveyings, melting, banburying after, to the die head extruding pelletization.
Further, wherein when described melt blending carries out in twin screw extruder, each of described twin screw extruder section temperature and die head temperature are set as follows: first district's temperature range is at 100 ℃ ~ 160 ℃, the Second Region temperature range is at 165 ~ 200 ℃, the 3rd district's temperature range is at 170 ~ 210 ℃, the die head temperature scope is at 110 ~ 160 ℃, rotating speed 20-50r/min.
Further, wherein when described melt blending carries out in single screw extrusion machine, each of described single screw extrusion machine section temperature and die head temperature are set as follows: first district's temperature range is at 100 ℃ ~ 160 ℃, the Second Region temperature range is at 165 ~ 200 ℃, the 3rd district's temperature range is at 170 ~ 210 ℃, the die head temperature scope is at 110 ~ 160 ℃, and rotating speed is 15-40r/min.
Further, the blending temperature of wherein said Banbury mixer is 175 ℃, and blend time 5min, rotating speed are 35r/min.
Further, district's temperature of wherein said single screw extrusion machine is 100 ℃, and two district's temperature are 175 ℃, and three district's temperature are 180 ℃, and die head temperature is 150 ℃, and rotating speed is 25r/min.
The optimal process for preparing described melt spraying non-woven fabrics section is: raw material is at high-speed crush mixing machine mixing 0.5min; The blending temperature of Banbury mixer is 175 ℃, and blend time 5min, rotating speed are 35r/min; The blend masterbatch that banburying makes is pulverized 0.5min in the high-speed mixing pulverizer; One district's temperature of single screw extrusion machine is 100 ℃, and two district's temperature are 175 ℃, and three district's temperature are 180 ℃, and die head temperature is 150 ℃, and rotating speed is 25r/min; The mass parts of each component is preferably: poly (propylene carbonate) is 80 parts, the section of polypropylene melt blown non-woven fabric is 20 parts, 25 parts of nano-calcium carbonates, 2 parts of maleic anhydride inoculated polypropylenes, maleic anhydride are 1 part, dicumyl peroxide is 0.01 part, nano silicon is 1 part, and erucic acid phthalein amine is 1 part, and oxalic acid is 0.5 part, when the st-yrax monoalky lether was 0.2 part, biodegradable melt spraying non-woven fabrics section had better mechanical property, thermal property and degradation property.
The present invention has following beneficial effect:
The tensile strength of the biodegradable melt spraying non-woven fabrics section of the present invention's preparation reaches as high as 25.86MPa, elongation at break reaches as high as 165.26%, melt flow rate (MFR) can reach 800-3000g/10min, second-order transition temperature reaches as high as 28.37 ℃, and 5% heat decomposition temperature reaches as high as 260 ℃;
Biodegradable melt spraying non-woven fabrics section provided by the present invention can be widely used in preparing the materials such as biodegradable melt spraying non-woven fabrics, melt-blown filter, SMS non-woven fabrics.
Embodiment
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
(Inner Mongol Meng Xi new and high technology group company provides poly (propylene carbonate) used in the embodiment of the invention, powder, BiOCO
2 TM100), number-average molecular weight is 71844Da, molecular weight distribution 1.82, tensile strength 4.7MPa, elongation at break 991.23%, 25 ℃ of second-order transition temperatures.
Used polypropylene melt blown non-woven fabric section (Shanghai Yi Shitong new material development company limited in the embodiment of the invention, section, trade mark P6815), number-average molecular weight is 45000Da, molecular weight distribution 1.16,162 ℃ of fusing points, molten mass flow rate 1243g/10min (230 ℃ of experimental temperatures, standard load 2160g).
Below the present invention will be further described by specific embodiment.
Embodiment 1
Take by weighing each component by following mass parts:
90 parts of poly (propylene carbonate)s; 10 parts of polypropylene melt blown non-woven fabric sections; 20 parts of nano-calcium carbonates; 2 parts of maleic anhydride inoculated polypropylenes; 0.5 part of maleic anhydride; 0.01 part of dicumyl peroxide; 1 part of nano silicon; 1 part of erucic acid phthalein amine; 0.5 part of citric acid; 0.2 part of st-yrax monoalky lether.
Preparation technology is as follows:
With above-mentioned each component 50 ℃ of dryings 6 hours (because poly (propylene carbonate) easily absorbs water, in drying process, for preventing that it from absorbing water again, can put into some potassium hydroxide as being water-retaining agent) in baking oven.Dried each component is mixed in proportion 0.5min and is placed on melt blending in the Banbury mixer in high speed disintegrator, blending temperature is 175 ℃, and the blend time is 5min, and rotating speed is 35r/min, namely gets the blend masterbatch.
Then the blend masterbatch is pulverized 0.5min with high speed disintegrator, make powder and be placed on the single screw extrusion machine extruding pelletization.
Wherein, forcing machine length-to-diameter ratio: 35:1; The forcing machine rotating speed is 25r/min.
Temperature arranges as follows:
One district: 100 ℃
Two districts: 175 ℃
Three districts: 180 ℃
Die head: 150 ℃
The mechanical property of this biodegradable melt spraying non-woven fabrics section adopts the test of xlw intelligence minor pulling experiment machine, specimen size is as follows: length is 100 ± 5mm, width is 10 ± 2mm, thickness is 1 ± 0.2mm, trial speed 500mm/min, experiment repeats 3 ~ 5 times, averages, namely get the tensile strength of described melt spraying non-woven fabrics section, elongation at break.The mechanical performance data of measuring sees Table 1.
Embodiment 2
Take by weighing each component by following mass fraction:
80 parts of poly (propylene carbonate)s; 20 parts of polypropylene melt blown non-woven fabric sections; 25 parts of nano-calcium carbonates; 2 parts of maleic anhydride inoculated polypropylenes; 1 part of maleic anhydride; 0.01 part of dicumyl peroxide; 1 part of nano silicon; 1 part of erucic acid phthalein amine; 0.5 part of oxalic acid; 0.2 part of st-yrax monoalky lether.
Preparation technology is as follows:
With above-mentioned each component 50 ℃ of dryings 6 hours (because poly (propylene carbonate) easily absorbs water, in drying process, for preventing that it from absorbing water again, can put into some potassium hydroxide as water-retaining agent) in baking oven.Dried each component is mixed in proportion 0.5min and is placed on melt blending in Banbury mixer in high speed disintegrator, blending temperature is 175 ℃, and the blend time is 5min, and rotating speed is 35r/min, namely gets the blend masterbatch.
Then the blend masterbatch is pulverized 0.5min with high speed disintegrator, make powder and be placed on the single screw extrusion machine extruding pelletization.
Wherein, forcing machine length-to-diameter ratio: 35:1; The forcing machine rotating speed is 25r/min.
Temperature arranges as follows:
One district: 100 ℃
Two districts: 175 ℃
Three districts: 180 ℃
Die head: 150 ℃
The mechanical property of this biodegradable melt spraying non-woven fabrics section adopts the test of xlw intelligence minor pulling experiment machine, specimen size is as follows: length is 100 ± 5mm, width is 10 ± 2mm, thickness is 1 ± 0.2mm, trial speed 500mm/min, experiment repeats 3 ~ 5 times, averages, namely get the tensile strength of this melt spraying non-woven fabrics section, elongation at break.The mechanical performance data of measuring sees Table 1.
Embodiment 3
Take by weighing each component by following mass fraction:
70 parts of poly (propylene carbonate)s; 30 parts of polypropylene melt blown non-woven fabric sections; 28 parts of nano-calcium carbonates; 3 parts of maleic anhydride inoculated polypropylenes; 1 part of Di-n-Butyl Amine; 0.01 part of benzoyl peroxide; 1 part in zinc oxide; 1 part of oleic acid phthalein amine; 0.3 part of oxalic acid; 0.2 part of benzophenone.
Preparation technology is as follows:
With above-mentioned each component 50 ℃ of dryings 6 hours (because poly (propylene carbonate) easily absorbs water, in drying process, for preventing that it from absorbing water again, can put into some potassium hydroxide as water-retaining agent) in baking oven.Dried each component is to mix 0.5min in the high speed disintegrator to be placed on melt blending in Banbury mixer at the high-speed mixing pulverizer in proportion, and blending temperature is 175 ℃, and the blend time is 5min, and rotating speed is 35r/min, namely gets the blend masterbatch.
Then the blend masterbatch is pulverized 0.5min with high speed disintegrator, make powder and be placed on the single screw extrusion machine extruding pelletization.
Wherein, forcing machine length-to-diameter ratio: 35:1; The forcing machine rotating speed is 25r/min.
Temperature arranges as follows:
One district: 100 ℃
Two districts: 175 ℃
Three districts: 180 ℃
Die head: 150 ℃
The mechanical property of this biodegradable melt spraying non-woven fabrics section adopts the test of xlw intelligence minor pulling experiment machine, specimen size is as follows: length is 100 ± 5mm, width is 10 ± 2mm, thickness is 1 ± 0.2mm, trial speed 500mm/min, experiment repeats 3 ~ 5 times, averages, namely get the tensile strength of this melt spraying non-woven fabrics section, elongation at break.The mechanical performance data of measuring sees Table 1.
Embodiment 4
Take by weighing each component by following mass fraction:
60 parts of poly (propylene carbonate)s; 40 parts of polypropylene melt blown non-woven fabric sections; 22 parts of nano imvites; 2 parts of maleic anhydride-styrene graft polypropylenes; 1 part of maleic anhydride; 0.06 part of dicumyl peroxide; 1 part of nano silicon; 1 part of erucic acid phthalein amine; 0.6 part of citric acid; 0.3 part of benzophenone.
Preparation technology is as follows:
With above-mentioned each component 50 ℃ of dryings 6 hours (because poly (propylene carbonate) easily absorbs water, in drying process, for preventing that it from absorbing water again, can put into some potassium hydroxide as water-retaining agent) in baking oven.Dry rear each component is mixed in proportion 0.5min and is placed on melt blending in Banbury mixer in high speed disintegrator, blending temperature is 175 ℃, and the blend time is 5min, and rotating speed is 35r/min, namely gets the blend masterbatch.
Then the blend masterbatch is pulverized 0.5min with high speed disintegrator, make behind the powder in the single screw extrusion machine extruding pelletization.
Wherein, forcing machine length-to-diameter ratio: 35:1; The forcing machine rotating speed is 25r/min.
Temperature arranges as follows:
One district: 100 ℃
Two districts: 175 ℃
Three districts: 180 ℃
Die head: 150 ℃
The mechanical property of this biodegradable melt spraying non-woven fabrics section adopts the test of xlw intelligence minor pulling experiment machine, specimen size is as follows: length is 100 ± 5mm, width is 10 ± 2mm, thickness is 1 ± 0.2mm, trial speed 500mm/min, experiment repeats 3 ~ 5 times, averages, namely get the tensile strength of this melt spraying non-woven fabrics section, elongation at break.The mechanical performance data of measuring sees Table 1.
The melt flow rate (MFR) of this biodegradable melt spraying non-woven fabrics section is to adopt the RL218-Melt Flow Rate Measurer to measure, 230 ℃ of experimental temperatures, and nominal load 2160g, the melting index data see Table 1.
The thermogravimetric analysis (TG) of this biodegradable melt spraying non-woven fabrics section is to carry out at NETZSCH TG209 thermogravimetric analyzer, and the about sample of 10mg is packed in the thermobalance sample pool, passes into high-purity N
2Purge, from room temperature (30 ℃), be warming up to 500 ℃ with the temperature rise rate of 10 ℃/min, 5% heat decomposition temperature data see Table 1.
The differential scanning calorimetric analysis (DSC) of this biodegradable melt spraying non-woven fabrics section carries out at NETZSCH DSC204 thermal analyzer.10 ℃/min of sweep velocity, Range of measuring temp-50 ℃ is to 200 ℃, and the second-order transition temperature data see Table 1.
Degradation property phosphate buffered saline buffer (10.5mL, the 0.2mol/L NaH of this biodegradable melt spraying non-woven fabrics section
2PO
4And 90.5mL, 0.2mol/L NaHPO
4Formulated, pH=7.7) to measure, it is that the title quality was m after the sheet of 0.5cmx0.5cm was dried to constant weight that section is cut into area
0, place the phosphate buffered saline buffer of pH=7.7, place 60 ℃ of constant temperature oil baths to add thermal destruction.Change a phosphate buffered saline buffer every 6 days, guarantee the relatively stable of pH.Sample took out every 6 days, with distilled water flushing material repeatedly, was dried to constant weight, the title quality is m
gRepresent degradation rate with rate of weight loss: rate of weight loss=(m
0-m
g)/m
0* 100%.The degraded situation of this biodegradable melt spraying non-woven fabrics section the results are shown in Table 2.
The performance of the section of table 1 polypropylene melt blown non-woven fabric and case study on implementation 1 ~ 4
The degradation property of the section of table 2 polypropylene melt blown non-woven fabric and case study on implementation 1 ~ 4
As shown in Table 1, adding along with the section of polypropylene melt blown non-woven fabric, the tensile strength first increases and then decreases, at poly (propylene carbonate): polypropylene melt blown non-woven fabric chipping qualities reaches than for 8:2 the time and is 25.86MPa to the maximum, has improved about 5 times than the tensile strength of pure poly (propylene carbonate).And the fracture extensibility reduces gradually, this is because polypropylene melt blown non-woven fabric section property is crisp, so add too much polypropylene melt blown non-woven fabric section the keeping of extensibility that be unfavorable for rupturing, at poly (propylene carbonate): polypropylene melt blown non-woven fabric chipping qualities is than for 8:2 the time, and the fracture extensibility maintains more than 100%.The melting index of embodiment 1-4 is along with the adding of polypropylene melt blown non-woven fabric section reduces gradually, but the melting index of all cutting into slices greater than the polypropylene melt blown non-woven fabric that melts and sprays usefulness can be used as melting and spraying material.The second-order transition temperature maximum reaches 28.37 ℃, increases than the glass transition temp of poly (propylene carbonate).Heat decomposition temperature T
-5%The adding of cutting into slices along with the polypropylene melt blown non-woven fabric raises gradually, illustrates that thermostability is improved.
As shown in Table 2, in phosphoric acid buffer 24 days, polypropylene melt blown non-woven fabric section degradation rate was 0, does not substantially degrade.24 days 5.1%, embodiment 1-4 that degraded of poly (propylene carbonate), along with the content of poly (propylene carbonate) increases, degradation rate increases, and along with the prolongation of time, degradation rate is first quick and back slow.Poly (propylene carbonate): when polypropylene melt blown non-woven fabric chipping qualities ratio was 8:2, degradation rate reached more than 4% in 24 days, had preferably degradation property.
In summary, the blending temperature of Banbury mixer is 175 ℃, and blend time 5min, rotating speed are 35r/min; One district's temperature of single screw extrusion machine is 100 ℃, and two district's temperature are 170 ℃, and three district's temperature are 180 ℃, and die head temperature is 150 ℃, and rotating speed is 25r/min; The mass fraction of each component: poly (propylene carbonate) is 80 parts, the section of polypropylene melt blown non-woven fabric is 20 parts, 25 parts of nano-calcium carbonates, 2 parts of maleic anhydride inoculated polypropylenes, maleic anhydride are 1 part, dicumyl peroxide is 0.01 part, nano silicon is 1 part, and erucic acid phthalein amine is 1 part, and oxalic acid is 0.5 part, when the st-yrax monoalky lether was 0.2 part, this biodegradable melt spraying non-woven fabrics section had better mechanical property, thermal property and degradation property.
Below only be the cited preferred embodiment of the present invention; be not to limit protection scope of the present invention; under the equivalence of using the present invention to do of those of ordinary skill in the technical field modify or change (goods such as the melt spraying non-woven fabrics for preparing with the biodegradable melt spraying non-woven fabrics section of the present invention, melt-blown filter, SMS non-woven fabrics), all with belonging to scope of patent protection of the present invention.
Claims (10)
1. a biodegradable melt spraying non-woven fabrics section is characterized in that, described melt spraying non-woven fabrics section is made by the material combination of following mass parts: poly (propylene carbonate) 50-90 part; Polypropylene melt blown non-woven fabric section 10-50 part; 0 ~ 40 part of nanoparticle; 0 ~ 10 part of expanding material; End-capping reagent 0-8 part; Initiator 0-0.1 part; 0 ~ 2 part of heat-resisting stabilizing agent; 0 ~ 2 part of slipping agent; 0 ~ 2 part of biodegradation promotor; 0 ~ 1 part of photolysis agent.
2. melt spraying non-woven fabrics section according to claim 1 is characterized in that, described melt spraying non-woven fabrics section is made by the material combination of following mass parts: 80 parts of poly (propylene carbonate)s; 20 parts of polypropylene melt blown non-woven fabric sections; 25 parts of nanoparticles; 2 parts of expanding materials; 1 part of end-capping reagent; 0.01 part of initiator; 1 part of heat-resisting stabilizing agent; 1 part of slipping agent; 0.5 part of biodegradation promotor; 0.2 part of photolysis agent.
3. melt spraying non-woven fabrics section according to claim 1 and 2 is characterized in that, the number-average molecular weight of described poly (propylene carbonate) is 40000-140000Da, second-order transition temperature T
gBe 19-25 ℃, tensile strength is 3-8MPa; The number-average molecular weight of described polypropylene melt-blown section is 30000-60000Da, is 230 ℃ of temperature in condition, melting index under the nominal load 2160g〉800g/10min.
4. melt spraying non-woven fabrics according to claim 1 and 2 section is characterized in that, described nanoparticle is at least a in the following substances: nano-calcium carbonate, nano barium sulfate or nano imvite; Described expanding material is at least a in the following substances: maleic anhydride inoculated polypropylene, glycidyl methacrylate-styrene-grafted polypropylene, maleic anhydride-styrene graft polypropylene or styrene-grafted polypropylene.
5. melt spraying non-woven fabrics according to claim 1 and 2 section is characterized in that, described end-capping reagent is at least a in the following substances: maleic anhydride, methyl alcohol, phthalic anhydride, naphthalene acid anhydride or Di-n-Butyl Amine; Described initiator is at least a in the following substances: benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, di-t-butyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate or di-cyclohexylperoxy dicarbonate.
6. melt spraying non-woven fabrics according to claim 1 and 2 section is characterized in that, described heat-resisting stabilizing agent is at least a in the following substances: polynite, nano silicon, kaolin or zinc oxide; Described slipping agent is at least a in the following substances: erucic acid phthalein amine, stearic phthalein amine, Zinic stearas or oleic acid phthalein amine.
7. melt spraying non-woven fabrics according to claim 1 and 2 section is characterized in that, described biodegradation promotor is at least a in the following substances: oxalic acid or citric acid; Described photolysis agent is at least a in the following substances: st-yrax monoalky lether, thioxanthone, benzophenone, benzoin dimethylether or 1-hydroxy-cyclohexyl phenyl ketone.
8. the preparation method of a biodegradable melt spraying non-woven fabrics section, it is characterized in that, with claim 1, each component is behind dry 6-12h under 45-55 ℃ the condition in 2, in high-speed mixer, mix according to the above ratio 0.5-3min, then melt blending in mixing facilities, blending temperature is 100-210 ℃, the blend time is 3-8min, rotating speed is 15-50r/min, afterwards blend is pulverized 0.5-3min in high-speed mixer, pulverizing is passed through single screw rod or twin screw extruder extruding pelletization, extruder temperature 100-210 ℃ after making powder, rotating speed is 15-50 r/min, obtains described melt spraying non-woven fabrics section.
9. method according to claim 8 is characterized in that, described high-speed mixer is high speed disintegrator; Described mixing facilities is Banbury mixer, single screw extrusion machine or twin screw extruder.
10. method according to claim 9, it is characterized in that, when described melt blending carries out in twin screw extruder, the process of described melt blending is as follows: with the hopper blanking of mixed described each component from twin screw extruder, pellet is extruded from a district, arrives the die head extrusion moulding through two districts, three districts; Each of described twin screw extruder section temperature and die head temperature are set as follows: first district's temperature range is at 100 ℃ ~ 160 ℃, the Second Region temperature range is at 165 ~ 200 ℃, the 3rd district's temperature range is at 170 ~ 210 ℃, and the die head temperature scope is at 110 ~ 160 ℃, rotating speed 20-50 r/min; When described melt blending carries out in single screw extrusion machine, each of described single screw extrusion machine section temperature and die head temperature are set as follows: first district's temperature range is at 100 ℃ ~ 160 ℃, the Second Region temperature range is at 165 ~ 200 ℃, the 3rd district's temperature range is at 170 ~ 210 ℃, the die head temperature scope is at 110 ~ 160 ℃, and rotating speed is 15-40 r/min.
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| CN103756127A (en) * | 2013-11-27 | 2014-04-30 | 芜湖跃飞新型吸音材料股份有限公司 | LLDPE modified isotatic polypropylene non-woven fabric and preparation method thereof |
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| CN104017348A (en) * | 2014-06-20 | 2014-09-03 | 江苏兆鋆新材料股份有限公司 | Polypropylene carbonate modified composite material and preparation method thereof |
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| CN104017348A (en) * | 2014-06-20 | 2014-09-03 | 江苏兆鋆新材料股份有限公司 | Polypropylene carbonate modified composite material and preparation method thereof |
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| CN108587090A (en) * | 2018-04-12 | 2018-09-28 | 海南大学 | Biodegradable antistatic polylactic acid non-woven fabrics slice of one kind and preparation method thereof |
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| CN111648039A (en) * | 2020-05-25 | 2020-09-11 | 界首市天鸿新材料股份有限公司 | Production process of green environment-friendly polypropylene melt-blown fabric |
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