CN109651706B - Hydrophilic lubricating auxiliary agent master batch, preparation method thereof and hydrophilic self-lubricating high polymer material containing hydrophilic lubricating auxiliary agent master batch - Google Patents
Hydrophilic lubricating auxiliary agent master batch, preparation method thereof and hydrophilic self-lubricating high polymer material containing hydrophilic lubricating auxiliary agent master batch Download PDFInfo
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- CN109651706B CN109651706B CN201811591019.2A CN201811591019A CN109651706B CN 109651706 B CN109651706 B CN 109651706B CN 201811591019 A CN201811591019 A CN 201811591019A CN 109651706 B CN109651706 B CN 109651706B
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- lubricating
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Abstract
The invention provides a hydrophilic lubricating auxiliary master batch, a preparation method thereof and a hydrophilic self-lubricating high polymer material containing the same. The hydrophilic lubricating auxiliary master batch comprises the following components in percentage by weight: 20-93% of amphiphilic oligomer, 2-30% of hydrophilic polymer material and 5-50% of hydrophobic polymer material; the amphiphilic oligomer comprises a hydrophilic segment and a lipophilic segment, the number average molecular weight of the hydrophilic segment is 300-3000, and the number average molecular weight of the lipophilic segment is 300-3000. The hydrophilic self-lubricating high polymer material comprises 60-99 parts by weight of a high polymer matrix material and 1-40 parts by weight of a hydrophilic lubricating auxiliary master batch. The hydrophilic lubricating additive master batch provided by the invention can effectively improve the hydrophilic lubricating property of the high polymer material, has a durable lubricating effect, and the hydrophilic self-lubricating high polymer material containing the hydrophilic lubricating additive master batch can be directly molded to prepare medical instruments without coating a self-lubricating coating or a lubricating agent.
Description
Technical Field
The invention belongs to the technical field of medical high polymer materials, and particularly relates to a hydrophilic lubricating auxiliary master batch, a preparation method thereof and a hydrophilic self-lubricating high polymer material containing the same.
Background
Polymeric medical devices (e.g., catheters, indwelling needles, etc.) play an important role in the diagnosis and treatment of disease. Some medical devices are used by contacting with body fluid or blood in a humid environment, and when entering into the human body, they rub against the tissues of the human body. Such medical devices are often required to have excellent lubricity in order to reduce friction, reduce tissue damage and improve operator operability.
The lubrication modification of the polymer medical apparatus mainly comprises two methods of physical modification and chemical modification. Physical modification means physical application of a lubricious coating prior to use. For example, CN 202909253U discloses a self-lubricating type antibacterial medical catheter, which is prepared by mixing acetal polymer, hydrophilic polymer, citrate plasticizer and organic solvent, stirring thoroughly, dissolving completely to form uniform hydrophilic coating solution, immersing the medical catheter in the hydrophilic coating solution, air drying the catheter with hydrophilic coating, and drying to form a stable coating on the surface of the medical catheter. CN1537643A discloses a medical lubricating fluid capable of being coated on the surface of a medical catheter to reduce friction resistance, which is divided into 1# (cellulose esters, adhesive polymers and plasticizers) and 2# (hydrophilic polymers and cellulose esters), and the medical lubricating fluid can be coated on the medical catheter in sequence to reduce the friction coefficient by 78%.
The chemical modification method is mainly to graft hydrophilic material on the surface of medical apparatus by plasma treatment or radiation. For example, CN 102264403a discloses a medical device having a lubricating surface when wet, in which a compound having a thiol group is supported on the surface of the medical device by irradiating ionized gas plasma, and then reacted with a hydrophilic polymer having a reactive group such as glycidyl methacrylate to form a lubricating coating. CN 104177641a discloses a method for preparing a lubricating coating on the surface of a medical polyvinyl chloride material, which comprises pretreating the medical polyvinyl chloride material by ozone, ion sputtering or ultraviolet irradiation, and then grafting the medical polyvinyl chloride material with hydrophilic materials such as acrylamide, N-dimethylacrylamide, N-vinylpyrrolidone, polyvinylpyrrolidone, polyethylene oxide, hydroxyethyl methacrylate, hydroxyethyl acrylate or polyvinyl alcohol under an oxygen-free condition to form the lubricating coating.
However, the coating formed by the physical modification method has low adhesive force and is easy to fall off; the coating formed by the chemical modification method inevitably contains toxic substances such as organic solvents, photoinitiators, reaction additives and the like. Moreover, both of the above methods make the production and use of medical devices more complicated, and the cost of economy and time is higher, which needs to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydrophilic lubricating auxiliary master batch, a preparation method thereof and a hydrophilic self-lubricating high polymer material containing the same. The hydrophilic lubricating additive master batch can effectively improve the hydrophilic lubricating property of the high polymer material, has a durable lubricating effect, and the hydrophilic self-lubricating high polymer material containing the hydrophilic lubricating additive master batch can be directly molded to prepare medical instruments without coating a self-lubricating coating or a lubricant.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a hydrophilic lubricating additive masterbatch, comprising the following components in percentage by weight:
20-93% of amphiphilic oligomer;
2-30% of hydrophilic polymer material;
5-50% of hydrophobic polymer material;
the amphiphilic oligomer comprises a hydrophilic segment and a lipophilic segment, the number average molecular weight of the hydrophilic segment is 300-3000, and the number average molecular weight of the lipophilic segment is 300-3000.
The invention adopts amphiphilic oligomer, hydrophilic polymer material and hydrophobic polymer material in specific proportion to mutually cooperate as a hydrophilic lubricating auxiliary agent, after the hydrophilic lubricating auxiliary agent is blended with a polymer matrix material, the amphiphilic oligomer can be greatly gathered on the surface of the material, the oleophylic chain segment of the amphiphilic oligomer is inserted into the material matrix, and the hydrophilic chain segment is exposed on the surface, so that a hydrophilic surface is formed, the self-lubricating effect can be realized only by wetting with water, and the step of coating a hydrophilic self-lubricating coating or a lubricating agent after the material is formed is avoided.
In the present invention, the weight percentage of the amphiphilic oligomer may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 72%, 73%, 75%, 76%, 78%, 80%, 82%, 83%, 85%, 88%, 90%, 93%, or the like.
The hydrophilic polymer material may be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 13%, 15%, 16%, 18%, 20%, 22%, 23%, 25%, 28%, 30%, or the like, in weight percentage.
In the invention, the main function of the hydrophilic polymer material is to reduce the migration rate of the amphiphilic oligomer and improve the compatibility and stability of the hydrophilic lubricating auxiliary master batch. If the amount of the hydrophilic lubricating additive is too much, the lubricating effect of the hydrophilic lubricating additive master batch on the hydrophilic self-lubricating high polymer material can be reduced, so that the friction coefficient of the hydrophilic self-lubricating high polymer material under a humid condition is improved; if the amount is too small, the amphiphilic oligomer may be unevenly dispersed in the hydrophilic lubricating aid masterbatch, may migrate to the surface too quickly in the hydrophilic self-lubricating polymeric material, or may be seriously precipitated.
The weight fraction of the hydrophobic polymeric material may be 5%, 8%, 10%, 12%, 13%, 15%, 16%, 18%, 20%, 22%, 23%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, or the like.
The molecular weight of the hydrophilic segment in the amphiphilic oligomer may be 300, 400, 500, 600, 700, 800, 900, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, or 3000, and the like.
The molecular weight of the lipophilic segment of the amphiphilic oligomer may be 300, 400, 500, 600, 700, 800, 900, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, or 3000, and the like.
When the molecular weight of the hydrophilic chain segment of the amphiphilic oligomer is too large and the molecular weight of the lipophilic chain segment is too small, the amphiphilic oligomer is unevenly dispersed in the hydrophilic lubricating auxiliary agent master batch and migrates to the surface too fast in the hydrophilic self-lubricating high polymer material or a precipitation phenomenon occurs; when the molecular weight of the hydrophilic chain segment is too small and the molecular weight of the lipophilic chain segment is too large, the lubricating effect of the hydrophilic lubricating auxiliary agent master batch on the hydrophilic self-lubricating high polymer material can be reduced, so that the friction coefficient of the hydrophilic self-lubricating high polymer material under the wet condition is improved.
As a preferred technical scheme of the invention, the hydrophilic lubricating auxiliary master batch comprises the following components in percentage by weight:
70-85% of amphiphilic oligomer;
2-10% of hydrophilic polymer material;
10-25% of hydrophobic polymer material.
In a preferred embodiment of the present invention, the hydrophilic segment of the amphiphilic oligomer is a polyethylene glycol chain or a polypropylene glycol chain.
Preferably, the number average molecular weight of the hydrophilic segment of the amphiphilic oligomer is 500-1500.
Preferably, the lipophilic segment of the amphiphilic oligomer is an alkyl chain.
Preferably, the amphiphilic oligomer has a lipophilic segment with a number average molecular weight of 500-1500.
In the present invention, the amphiphilic oligomer may be a commercially available product, or may be prepared by the following method:
mixing hydrophilic oligomer and halogenated alkane according to a preset molar ratio (the selectable molar ratio is 1:2-2:1, such as 1:1, 1:2 or 2:1, but not limited to the listed ratio, and other ratios within the range can be selected), adding the mixture into a sodium hydroxide solution, heating the mixture to boiling, carrying out condensation reflux reaction for more than 5 hours, adding excessive hydrochloric acid for neutralization, and carrying out distillation purification to obtain the amphiphilic oligomer; according to different types and proportions of raw materials, amphiphilic oligomers with the following different structures can be obtained:
structural formula 1: h3C-(CH2CH2O)n-(CH2)m-CH3The raw material is H3C-(CH2CH2O)n-H and halogenated alkane CH3(CH2)mX (X is halogen) and the molar ratio of the two is 1: 1;
structural formula 2: HO- (CH)2CH2O)n-(CH2)m-(OCH2CH2)d-OH, starting from HO- (CH)2CH2O)n-H、HO-(CH2CH2O)d-H and halogenated alkane X- (CH)2)mX, wherein the molar ratio of the three is 1:1: 1;
structural formula 3: h3C-(CH2)m-(OCH2CH2)n-O-(CH2)e-CH3The raw material is HO- (CH)2CH2O)n-H、CH3(CH2)mX and CH3(CH2)eX, wherein the molar ratio of the three is 1:1: 1;
structural formula 4: h3C-[CH2CH(CH3)O]n-(CH2)m-CH3The raw material is H3C-[CH2CH(CH3)O]n-H and halogenated alkane CH3(CH2)mX (X is halogen) and the molar ratio of the two is 1: 1;
structural formula 5: HO- [ CH2CH(CH3)O]n-(CH2)m-[OCH(CH3)CH2]d-OH, starting from HO- (CH)2CH(CH3)O)n-H、HO-(CH2CH(CH3)O)d-H and halogenated alkane X- (CH)2)mX, wherein the molar ratio of the three is 1:1: 1;
structural formula 6: h3C-(CH2)m-[OCH(CH3)CH2]n-O-(CH2)e-CH3The raw material is HO- [ CH2CH(CH3)O]n-H、CH3(CH2)mX and CH3(CH2)eX, wherein the molar ratio of the three is 1:1: 1;
wherein n and d are each independently an integer from 5 to 65, and may be, for example, 5, 8, 10, 12, 15, 18, 20, 22, 25, 30, 35, 40, 45, 50, 55, 60, 65, or the like; the preferred range is 10-25;
each of the m and e values is independently an integer from 20 to 215, and may be, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 120, 130, 150, 160, 180, 200, 210, 215, or the like; the preferred range is 35-110;
x is a halogen element, and can be fluorine, chlorine, bromine or iodine.
As a preferred technical solution of the present invention, the hydrophilic polymer material is selected from one or a combination of at least two of polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone or methyl ethylene oxide-siloxane copolymer; typical but non-limiting examples of such combinations are: combinations of polyethylene glycol and polypropylene glycol, polyethylene glycol and polyvinylpyrrolidone, polyethylene oxide and polyvinylpyrrolidone, polyethylene glycol and methyl ethylene oxide-siloxane copolymer, polypropylene glycol and polyvinylpyrrolidone, polyvinylpyrrolidone and methyl ethylene oxide-siloxane copolymer, and the like.
Preferably, the number average molecular weight of the hydrophilic polymer material is 1000-50000, and may be, for example, 1000, 2000, 3000, 4000, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, or 50000; further preferably 5000-.
As a preferred embodiment of the present invention, the hydrophobic polymer material is selected from the group consisting of polyolefin (e.g., polyethylene PE, polypropylene PP, etc.), Polycarbonate (PC), polyester (e.g., polyethylene terephthalate PET, polybutylene terephthalate PBT, polyethylene terephthalate-1, 4-cyclohexanedimethanol PETG, polylactic acid PLA, polyester elastomer TPEE, etc.), nylon (PA), Cyclic Olefin Copolymer (COC), ethylene-vinyl acetate copolymer (EVA, acrylonitrile-butadiene-styrene block copolymer (ABS), acrylate-styrene-acrylonitrile graft copolymer (ASA), styrene-acrylonitrile copolymer (SAN), polyether block amide (PEBA), styrene-based elastomer (e.g., styrene-butadiene-styrene block copolymer, SBS, polypropylene copolymer, etc.), styrene-acrylonitrile copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polyether block amide (PEBA), styrene-based elastomer (e.g., styrene-butadiene-styrene block copolymer, SBS, styrene-butadiene-styrene block copolymer, styrene-styrene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-styrene block copolymer, styrene-styrene block copolymer, styrene-styrene block copolymer, styrene-copolymer, poly (SAN), and the like, Hydrogenated styrene-butadiene-styrene block copolymer SEBS, styrene-isoprene-styrene block copolymer SIS, hydrogenated styrene-isoprene-styrene block copolymer SEPS, hydrogenated styrene-butadiene/isoprene-styrene block copolymer SEEPS, etc.), polyolefin elastomer, polyurethane elastomer (TPU), polyester elastomer, dynamically vulcanized blend type thermoplastic elastomer (TPV), interpenetrating polymer network type thermoplastic elastomer (IPN-TPS), or silicone rubber, or a mixture of at least two thereof.
In a second aspect, the present invention provides a method for preparing the above hydrophilic lubricating additive masterbatch, comprising the following steps:
(1) mixing a hydrophilic polymer material and a hydrophobic polymer material to form a premix;
(2) and (2) melting and blending the premix obtained in the step (1) and the amphiphilic oligomer to obtain the hydrophilic lubricating auxiliary agent master batch.
As a preferred embodiment of the present invention, the mixing in step (1) is carried out in a high-speed mixer.
Preferably, the rotation speed of the high-speed mixer is 300-500r/min, such as 300r/min, 320r/min, 350r/min, 380r/min, 400r/min, 420r/min, 450r/min, 480r/min or 500 r/min; the mixing time is 3-10min, such as 3min, 3.5min, 4min, 4.5min, 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10 min.
Preferably, the melt blending in step (2) is carried out in a twin screw extruder.
Preferably, the premix in step (2) is added from a rear feeding device of the twin-screw extruder, and the amphiphilic oligomer is added from a front feeding device of the twin-screw extruder.
Preferably, the barrel temperature of the twin-screw extruder is 130-300 ℃; for example, it may be 130 ℃, 150 ℃, 170 ℃, 180 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃. The barrel temperature of the twin-screw extruder mainly depends on the processing temperature range of the hydrophobic polymer material.
Preferably, the screw rotating speed of the double-screw extruder is 10-200 r/min; for example, it may be 10r/min, 20r/min, 50r/min, 80r/min, 100r/min, 120r/min, 150r/min, 180r/min, or 200 r/min.
In a third aspect, the invention provides a hydrophilic self-lubricating polymer material, which comprises the following components in parts by weight:
60-99 parts (for example, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 76 parts, 78 parts, 80 parts, 82 parts, 83 parts, 85 parts, 86 parts, 88 parts, 90 parts, 92 parts, 95 parts, 98 parts, or 99 parts, etc.) of a polymer base material and 1-40 parts (for example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, or 40 parts, etc.) of a hydrophilic lubricating aid masterbatch provided by the first aspect of the present invention.
As a preferable technical solution of the present invention, the hydrophobic polymer material in the polymer base material and the hydrophilic lubricating auxiliary master batch is the same kind of material or a material with good compatibility.
In the present invention, the same kind of material refers to a material having the same molecular structure (for example, two kinds of polyethylenes having different molecular weights) or a material having similar repeating units (for example, polyethylene terephthalate and polybutylene terephthalate in polyester) although the molecular structure is different. The material with good compatibility refers to a material capable of forming a macromolecular compatible system, and can be selected by a person skilled in the art according to experience.
Preferably, the hydrophilic self-lubricating high polymer material comprises the following components in parts by weight: 60-85 parts of a polymer matrix material and 15-40 parts of the hydrophilic lubricating assistant master batch provided by the first aspect of the invention.
Preferably, the hydrophilic self-lubricating polymer material further comprises 0.01-1 part (e.g., 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, etc.) of a stabilizer, and further preferably 0.05-0.5 part of a stabilizer.
In a fourth aspect, the invention provides a preparation method of the hydrophilic self-lubricating polymer material, which comprises the following steps:
(1) mixing a high-molecular base material, a hydrophilic lubricating auxiliary master batch and an optional stabilizer by a high-speed mixer to form a premix;
(2) and (2) blending and extruding the premix obtained in the step (1) through an extruder to obtain the hydrophilic self-lubricating high polymer material.
Wherein, the mixing in the step (1) can be carried out at normal temperature and at the rotating speed of 300-500r/min for 5-15 min;
the extruder in the step (2) can be a double-screw extruder, the diameter of a screw is 30-60mm, the length-diameter ratio of the screw is 30-50, the compression ratio of the screw is 2-4, the number of opening die holes is 1-8, the diameter of the opening die hole is 2-4mm, the rotation speed of the screw is 10-200rpm, and the blending temperature is the same as the processing temperature of the high polymer matrix material.
In a fifth aspect, the invention provides a use of the hydrophilic self-lubricating polymer material for medical instruments.
The hydrophilic self-lubricating polymer material provided by the invention can be used for manufacturing various medical instruments or medical instrument parts in various subsequent forming and processing modes. The subsequent forming process includes, but is not limited to, extrusion, injection molding, compression molding, blow molding, or the like. The self-lubricating effect of the formed products can be immediately realized only by wetting with water in the using process.
Compared with the prior art, the invention has the following beneficial effects:
the hydrophilic lubricating auxiliary agent master batch provided by the invention can be blended with a polymer matrix material to obtain a hydrophilic self-lubricating polymer material, and the hydrophilic self-lubricating polymer material is directly processed into a product with a hydrophilic self-lubricating effect, so that the problems that a large amount of lubricant needs to be additionally coated before the conventional polymer product with a hydrophilic lubricating requirement is used, or a hydrophilic self-lubricating coating and a cured coating need to be coated after secondary processing are solved.
After the hydrophilic self-lubricating high polymer material provided by the invention is wetted, the dynamic friction coefficient is below 0.07; and after the medical instrument is soaked in water for one month, the dynamic friction coefficient is not obviously changed, the hydrophilic self-lubricating effect is durable and effective, and the medical instrument can be used for preparing medical instruments.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The amphiphilic oligomer adopted in the embodiment of the invention is a self-made product, and the preparation method comprises the following steps: mixing polyethylene glycol or polypropylene glycol with halogenated alkane, adding the mixture into a sodium hydroxide solution, heating the mixture to boiling, carrying out condensation reflux reaction for 5 hours, then adding excessive hydrochloric acid for neutralization, and carrying out distillation purification to obtain the amphiphilic oligomer. Different amphiphilic oligomers can be obtained according to different types and proportions of raw materials, and the structure and the raw materials of each amphiphilic oligomer are as follows:
formula I: h3C-(CH2CH2O)6-(CH2)220-CH3
The raw material is H3C-(CH2CH2O)6-H and halogenated alkane CH3(CH2)220Br in a molar ratio of 1:1.
Formula II: h3C-(CH2CH2O)20-(CH2)160-CH3
The raw material is H3C-(CH2CH2O)20-H and halogenated alkane CH3(CH2)160Br in a molar ratio of 1:1.
Formula III: h3C-(CH2CH2O)30-(CH2)100-CH3
The raw material is H3C-(CH2CH2O)30-H and halogenated alkane CH3(CH2)100Br in a molar ratio of 1:1.
Formula IV: h3C-[CH2CH(CH3)O]45-(CH2)80-CH3
The raw material is H3C-[CH2CH(CH3)O]45-H and halogenated alkane CH3(CH2)80Br in a molar ratio of 1:1.
Formula V: h3C-[CH2CH(CH3)O]50-(CH2)60-CH3
The raw material is H3C-[CH2CH(CH3)O]50-H and halogenated alkane CH3(CH2)60Br in a molar ratio of 1:1.
Formula VI: h3C-[CH2CH(CH3)O]65-(CH2)20-CH3
The raw material is H3C-[CH2CH(CH3)O]65-H and halogenated alkane CH3(CH2)20Br in a molar ratio of 1:1.
Example 1
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 3 parts by weight of polyethylene glycol and 17 parts by weight of polypropylene into a high-speed mixer, and mixing for 10min at the rotating speed of 300r/min to form a premix;
(2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 80 parts by weight of the amphiphilic oligomer with the structure of the formula II from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 130 ℃ to 200 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating auxiliary agent master batch.
Preparing a hydrophilic self-lubricating high polymer material:
(a) adding 70 parts by weight of polypropylene, 30 parts by weight of the hydrophilic lubricating additive master batch provided by the embodiment and 0.5 part by weight of phosphite stabilizer into a high-speed mixer, and mixing at normal temperature and a rotating speed of 300r/min for 10min to form a premix;
(b) adding the premix obtained in the step (a) into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 45mm, the length-diameter ratio is 30:1, the temperature of each section of the charging barrel from a hopper to a neck die is 130 ℃, 170 ℃, 180 ℃, 200 ℃ and 200 ℃, and blending and extruding to obtain the hydrophilic self-lubricating high polymer material.
Example 2
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 5 parts by weight of polyethylene glycol and 15 parts by weight of nylon 12 into a high-speed mixer, and mixing for 10min at the rotating speed of 400r/min to form a premix;
(2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 80 parts by weight of the amphiphilic oligomer with the structure of the formula III from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 150 ℃ to 300 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating auxiliary agent master batch.
Preparing a hydrophilic self-lubricating high polymer material:
(a) adding 80 parts by weight of nylon 12, 20 parts by weight of the hydrophilic lubricating assistant master batch provided by the embodiment and 0.5 part by weight of phosphite stabilizer into a high-speed mixer, and mixing at normal temperature and a rotating speed of 300r/min for 10min to form a premix;
(b) adding the premix obtained in the step (a) into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 50mm, the length-diameter ratio is 45:1, the rotating speed of the screw is 150r/min, the temperatures of all sections of the charging barrel from a hopper to a neck die are respectively 150 ℃, 170 ℃, 240 ℃, 280 ℃, 300 ℃ and 300 ℃, and blending and extruding to obtain the hydrophilic self-lubricating polymer material.
Example 3
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 2 parts by weight of polyoxyethylene and 18 parts by weight of SEBS into a high-speed mixer, and mixing for 10min at the rotating speed of 300r/min to form a premix;
(2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 80 parts by weight of the amphiphilic oligomer with the structure shown in formula IV from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 130 ℃ to 200 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating auxiliary agent master batch.
Preparing a hydrophilic self-lubricating high polymer material:
(a) adding 60 parts by weight of SEBS/paraffin-based rubber oil mixture, 40 parts by weight of the hydrophilic lubricating aid master batch provided in the embodiment and 0.3 part by weight of phosphite stabilizer into a high-speed mixer, and mixing at normal temperature and a rotating speed of 300r/min for 10min to form a premix;
(b) adding the premix obtained in the step (a) into a double-screw extruder, wherein the diameter of a screw rod of the double-screw extruder is 45mm, the length-diameter ratio is 30:1, the rotating speed of the screw rod is 150r/min, the temperature of each section of the charging barrel from a hopper to a neck mold is 130 ℃, 170 ℃, 180 ℃, 200 ℃ and 200 ℃, and blending and extruding to obtain the hydrophilic self-lubricating high polymer material.
Example 4
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 3 parts by weight of polyoxyethylene and 17 parts by weight of polyethylene into a high-speed mixer, and mixing for 10min at the rotating speed of 300r/min to form a premix;
(2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 80 parts by weight of the amphiphilic oligomer with the structure shown in the formula V from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 130 ℃ to 200 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating auxiliary agent master batch.
Preparing a hydrophilic self-lubricating high polymer material:
80 parts by weight of a silica gel premix (comprising crude silica gel, a reinforcing filler, a structure control agent, a heat-resistant assistant and a coloring agent), 20 parts by weight of the hydrophilic lubricating assistant masterbatch provided in the embodiment and 0.4 part by weight of a stabilizer are thinned for 20 times, after blanking, oven heat treatment, remilling, adding a vulcanizing agent and then thinning, then standing overnight, remilling, discharging, and finally extruding and forming to obtain the hydrophilic self-lubricating polymer material.
Example 5
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 10 parts by weight of polyvinylpyrrolidone and 20 parts by weight of polylactic acid into a high-speed mixer, and mixing for 10min at the rotating speed of 300r/min to form a premix;
(2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 70 parts by weight of the amphiphilic oligomer with the structure of the formula III from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 130 ℃ to 200 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating auxiliary agent master batch.
Preparing a hydrophilic self-lubricating high polymer material:
(a) adding 75 parts by weight of polylactic acid, 25 parts by weight of the hydrophilic lubricating additive master batch provided in the embodiment and 0.5 part by weight of phosphite stabilizer into a high-speed mixer, and mixing at normal temperature and a rotating speed of 300r/min for 10min to form a premix;
(b) adding the premix obtained in the step (a) into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 50mm, the length-diameter ratio is 45:1, the rotating speed of the screw is 150r/min, the temperatures of all sections of the charging barrel from a hopper to a neck die are 130 ℃, 120 ℃, 170 ℃, 180 ℃, 200 ℃ and 200 ℃, and blending and extruding to obtain the hydrophilic self-lubricating polymer material.
Example 6
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 5 parts by weight of polyvinylpyrrolidone and 10 parts by weight of SBS into a high-speed mixer, and mixing for 10min at the rotating speed of 300r/min to form a premix;
(2) and (2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 85 parts by weight of the amphiphilic oligomer with the structure of the formula III from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 130 ℃ to 200 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating aid master batch.
Preparing a hydrophilic self-lubricating high polymer material:
(a) adding 80 parts by weight of SBS/paraffin-based rubber oil mixture, 20 parts by weight of the hydrophilic lubricating additive master batch provided in the embodiment and 0.3 part by weight of phosphite stabilizer into a high-speed mixer, and mixing at normal temperature and the rotating speed of 300r/min for 10min to form premix;
(b) adding the premix obtained in the step (a) into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 45mm, the length-diameter ratio is 30:1, the rotating speed of the screw is 150r/min, the temperature of each section of the charging barrel from a hopper to a neck die is 130 ℃, 170 ℃, 180 ℃, 200 ℃ and 200 ℃, and blending and extruding to obtain the hydrophilic self-lubricating polymer material.
Example 7
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 30 parts by weight of polyethylene oxide and 50 parts by weight of low-density polyethylene into a high-speed mixer, and mixing for 10min at the rotating speed of 300r/min to form a premix;
(2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 20 parts by weight of the amphiphilic oligomer with the structure shown in formula IV from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 130 ℃ to 200 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating auxiliary agent master batch.
Preparing a hydrophilic self-lubricating high polymer material:
(a) adding 70 parts by weight of low-density polyethylene, 30 parts by weight of the hydrophilic lubricating additive master batch provided in the embodiment and 0.5 part by weight of phosphite stabilizer into a high-speed mixer, and mixing at normal temperature and a rotating speed of 300r/min for 10min to form a premix;
(b) adding the premix obtained in the step (a) into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 45mm, the length-diameter ratio is 30:1, the temperature of each section of the charging barrel from a hopper to a neck die is 130 ℃, 170 ℃, 180 ℃, 200 ℃ and 200 ℃, and blending and extruding to obtain the hydrophilic self-lubricating high polymer material.
Example 8
The embodiment provides a hydrophilic self-lubricating auxiliary agent master batch and a hydrophilic self-lubricating high polymer material, and the preparation method comprises the following steps:
preparing a hydrophilic self-lubricating auxiliary agent master batch:
(1) adding 2 parts by weight of polyoxyethylene and 13 parts by weight of low-density polyethylene into a high-speed mixer, and mixing for 10min at the rotating speed of 300r/min to form a premix;
(2) and (2) adding the premix obtained in the step (1) from a rear-section feeding device of a double-screw extruder, adding 85 parts by weight of amphiphilic oligomer with the structure shown in formula IV from a front-section feeding device of the double-screw extruder, controlling the temperature of a charging barrel of the double-screw extruder to rise from 130 ℃ to 200 ℃ from a feeding section to a die, controlling the rotating speed of a screw to be 200r/min, and blending and extruding to obtain the hydrophilic lubricating auxiliary agent master batch.
Preparing a hydrophilic self-lubricating high polymer material:
(a) adding 85 parts by weight of polystyrene, 15 parts by weight of the hydrophilic lubricating additive master batch provided in the embodiment and 0.5 part by weight of phosphite stabilizer into a high-speed mixer, and mixing at normal temperature and a rotating speed of 300r/min for 10min to form a premix;
(b) adding the premix obtained in the step (a) into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 45mm, the length-diameter ratio is 30:1, the temperature of each section of the charging barrel from a hopper to a neck die is 130 ℃, 170 ℃, 180 ℃, 200 ℃ and 200 ℃, and blending and extruding to obtain the hydrophilic self-lubricating high polymer material.
Comparative example 1
The difference from example 3 is that 100 parts by weight of the SEBS/paraffin-based rubber oil mixture and 0.3 part by weight of the phosphite stabilizer were directly blended and extruded without adding a hydrophilic lubricating aid master batch.
Comparative example 2
The difference from the example 3 is that 100 weight parts of SEBS/paraffin-based rubber oil mixture and 0.3 weight part of phosphite stabilizer are directly blended, extruded and molded into a sheet without adding hydrophilic lubricating aid master batch, and a layer of hydrocarbon-based lubricating grease is coated on the surface of the sheet to serve as a surface lubricant.
Comparative example 3
The difference from example 1 is that the amphiphilic oligomer having the structure of formula II is replaced with the amphiphilic oligomer having the structure of formula I.
Comparative example 4
The difference from example 4 is that the amphiphilic oligomer having the structure of formula V is replaced with the amphiphilic oligomer having the structure of formula VI.
Comparative example 5
The difference from example 7 is that the hydrophilic self-lubricating auxiliary master batch is composed of 20 parts by weight of amphiphilic oligomer having the structure of formula IV, 35 parts by weight of hydrophilic polymer material and 45 parts by weight of hydrophobic polymer material.
Comparative example 6
The difference from example 1 is that the hydrophilic self-lubricating auxiliary masterbatch is composed of 80 parts by weight of amphiphilic oligomer having the structure of formula II and 20 parts by weight of hydrophobic polymeric material.
The polymer materials provided in the above examples and comparative examples were extrusion-molded into sheets, and their properties were tested according to the following methods:
(1) evaluation of hydrophilic self-lubricating effect and repeated use times: the coefficient of dynamic friction was determined by wetting the product surface and test glass plates with water according to ASTM G115-10; after drying, adding water again for wetting, measuring the dynamic friction coefficient, and comparing the front and back dynamic friction coefficients; after five times, the product enters purified water, and the condition that the dynamic friction coefficients are consistent and the repeatable times are recorded in a contrast manner; soaking the product in purified water, periodically changing water every day, and measuring the dynamic friction coefficient after one month;
(2) sensitization test: the test was carried out according to the method specified in GB/T16886.10-2011.
The results of the above performance tests are shown in table 1 below:
TABLE 1
Comparing the embodiment of the invention with the comparative examples 1-2, the hydrophilic lubricating auxiliary master batch provided by the invention can effectively reduce the dynamic friction coefficient of the polymer material after being wetted, the effect is better than that of an added lubricant, the hydrophilic self-lubricating polymer material prepared by the invention can be reused, the dynamic friction coefficient is not obviously changed after being wetted for a long time, and the hydrophilic self-lubricating polymer material has a durable lubricating effect. From comparative examples 3 to 4, it can be seen that when the molecular weight of the hydrophilic segment of the amphiphilic oligomer is too low and the molecular weight of the lipophilic segment is too high, the lubricating effect of the hydrophilic self-lubricating polymer material is obviously reduced; when the molecular weight of the hydrophilic chain segment of the amphiphilic oligomer is too high and the molecular weight of the lipophilic chain segment is too low, the stability of the hydrophilic self-lubricating high polymer material is reduced, and the repeated lubricating effect is reduced. From comparative examples 5 to 6, it is known that when the content of the hydrophilic polymer material is too large, the lubricating effect of the hydrophilic self-lubricating polymer material is remarkably reduced; when the content of the hydrophilic polymer material is too small, the stability of the hydrophilic self-lubricating polymer material is lowered, and the repeated lubrication effect is lowered.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (20)
1. The hydrophilic lubricating aid master batch is characterized by comprising the following components in percentage by weight:
20-93% of amphiphilic oligomer;
2-30% of hydrophilic polymer material;
5-50% of hydrophobic polymer material;
the amphiphilic oligomer comprises a hydrophilic chain segment and a lipophilic chain segment, the number average molecular weight of the hydrophilic chain segment is 300-3000, and the number average molecular weight of the lipophilic chain segment is 300-3000;
the hydrophilic chain segment of the amphiphilic oligomer is a polyethylene glycol chain or a polypropylene glycol chain;
the lipophilic chain segment of the amphiphilic oligomer is an alkyl chain.
2. The hydrophilic lubricating aid masterbatch according to claim 1 wherein the hydrophilic lubricating aid masterbatch comprises the following components in weight percent:
70-85% of amphiphilic oligomer;
2-10% of hydrophilic polymer material;
10-25% of hydrophobic polymer material.
3. The hydrophilic lubricating aid masterbatch of claim 1 wherein the hydrophilic segment of the amphiphilic oligomer has a number average molecular weight of 500-1500.
4. The hydrophilic lubricating aid masterbatch of claim 1 wherein the amphiphilic oligomer lipophilic segment has a number average molecular weight of 500-1500.
5. The hydrophilic lubricating additive masterbatch of claim 1 wherein the hydrophilic polymeric material is selected from one or a combination of at least two of polyethylene oxide, polypropylene glycol, polyvinylpyrrolidone or propylene oxide-siloxane copolymer.
6. The hydrophilic lubricating aid masterbatch according to claim 5, wherein the hydrophilic polymer material has a number average molecular weight of 1000-50000.
7. The hydrophilic lubricating aid masterbatch according to claim 5, wherein the hydrophilic polymer material has a number average molecular weight of 5000-.
8. The hydrophilic lubricating additive masterbatch of claim 1 wherein the hydrophobic polymeric material is selected from one or a mixture of at least two of polyolefin, polycarbonate, nylon, ethylene-vinyl acetate copolymer, polyether block amide, styrenic elastomer, polyurethane elastomer, dynamically vulcanized blend type thermoplastic elastomer, thermoplastic interpenetrating polymer network type elastomer, or silicone.
9. A process for preparing a hydrophilic lubricating aid masterbatch according to any one of claims 1 to 8, comprising the steps of:
(1) mixing a hydrophilic polymer material and a hydrophobic polymer material to form a premix;
(2) and (2) melting and blending the premix obtained in the step (1) and the amphiphilic oligomer to obtain the hydrophilic lubricating auxiliary agent master batch.
10. The method according to claim 9, wherein the mixing in step (1) is performed in a high-speed mixer.
11. The method as claimed in claim 10, wherein the rotation speed of the high-speed mixer is 300-500r/min, and the mixing time is 3-10 min.
12. The production method according to claim 10, wherein the melt blending in step (2) is carried out in a twin-screw extruder.
13. The method of claim 10, wherein the premix in the step (2) is fed from a rear feeding device of the twin-screw extruder, and the amphiphilic oligomer is fed from a front feeding device of the twin-screw extruder.
14. The method as claimed in claim 12, wherein the barrel temperature of the twin-screw extruder is 200-300 ℃.
15. The method as claimed in claim 12, wherein the twin-screw extruder has a screw rotation speed of 10 to 200 r/min.
16. The hydrophilic self-lubricating high polymer material is characterized by comprising the following components in parts by weight:
60-85 parts of a polymer matrix material and 15-40 parts of a hydrophilic lubricating aid master batch as claimed in any one of claims 1-8.
17. The hydrophilic self-lubricating polymeric material of claim 16, wherein the polymeric matrix material is the same kind of material as the hydrophobic polymeric material in the hydrophilic lubricating additive masterbatch.
18. The hydrophilic self-lubricating polymeric material of claim 17, further comprising 0.01 to 1 part by weight of a stabilizer.
19. The hydrophilic self-lubricating polymeric material of claim 18, wherein the stabilizer is 0.05 to 0.5 parts by weight.
20. Use of a hydrophilic self-lubricating polymeric material according to any one of claims 16 to 19 in a medical device.
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