CN109401216A - Polymer blend and functional layer and its preparation method and application - Google Patents
Polymer blend and functional layer and its preparation method and application Download PDFInfo
- Publication number
- CN109401216A CN109401216A CN201710703875.1A CN201710703875A CN109401216A CN 109401216 A CN109401216 A CN 109401216A CN 201710703875 A CN201710703875 A CN 201710703875A CN 109401216 A CN109401216 A CN 109401216A
- Authority
- CN
- China
- Prior art keywords
- polymer blend
- polyester
- weight
- repetitive unit
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention relates to polymeric material field, a kind of polymer blend and functional layer and its preparation method and application are disclosed.Specifically, on the basis of the total weight of each component, the polymer blend contains following components: (the polyester A, the polyester A of 150-98 weight % is the copolymer containing repetitive unit B shown in repetitive unit A shown in formula (I) and formula (II)；(2) the polyester B, the polyester B of 1-49 weight % is the copolymer containing repetitive unit B shown in repetitive unit C shown in formula (III) and formula (II)；(3) fiberfill of 1-49 weight %.Polymer blend of the invention has good low-temp plastic and shape-memory properties.Therefore, when polymer blend provided by the invention being used for protecting ware for sports, moulding can be carried out according to the difference of application site, so that protector is more bonded body, more comfortable and easy to make.
Description
Technical field
The present invention relates to polymeric material fields, and in particular, to a kind of polymer blend, the preparation of the polymer blend
Method and a kind of functional layer and preparation method thereof and their application.
Background technique
, all there is certain risk of injury during the motion, protecting ware for sports is in either amateurish or professional athlete
It is engaged in protector necessary to sports.Competition type movement needs for example, skidding, skiing, bicycle etc. move to human body
Head, extremities joint portion are protected；Countering type movement needs the head to human body for example, boxing, tae kwon do, fencing etc. move
Portion, body large area position (chest, waist, back, abdomen, crotch) etc. are protected.In fact, in addition to falling down, hitting, abrade
Outside unexpected injury, due to protector wear it is improper caused by occurs accident also very generally.Especially children, since it is in body
The growth phase of body, quickly, and difference is huge between Different Individual, is difficult to find entirely appropriate protector for pattern of body form change.
Protecting ware for sports is in the market, many kinds of at present, is broadly divided into soft protector and hard protector.Soft protector can be compared with
It good fitting body and breathes freely, certain support or limited effect is provided, muscle and ligament injury are prevented.Hard protector is usual
It is two layers or three layers, internal layer is bonded body, provides buffering, guarantees to breathe freely, outer layer is hard rigid material, is violently shaken in human body
When shock resistance and anti-scratch protection are provided.Currently, on the market the inner layer material of most of common hard protector with it is soft
Protective gear material is consistent, surrounds region by the fabric of cotton, spandex and elastic, plays fixed function, then in closing
The padded coamings such as interbed EVA or polyurethane, outermost layer provide shock resistance and scraping usually using PP or PE or ABS.This kind movement
The advantage of protector is that price is relatively cheap, and masses can receive.And the disadvantage is that, being not fixed firmly, during easy movement
It falls off or slides, or since the protected position shape cooperation of hard outer and body is bad cause to wear uncomfortable.
High-end protector on the market, the material of use cover many novel scientific and technological contents.Such as U.S. Dow
Corning company proposes a kind of new positive guard system (Active of patent shock resistant technique-Dow Corning
Protection System).It belongs to a kind of three-dimensional woven interval insulant handled by specific coatings, under normal circumstances
It is able to maintain soft and toughness, but moment is hardened when being hit.After impact force disappears, soft condition is recovered immediately.Britain D3O
Lab company develops a kind of special dress material.A kind of athletic protective helmet for having used D3O is mentioned in US0157083, is hit
When can be hardened rapidly, reducing impact force, then softens at once whereby, and without limitation on the flexibility of wearing personnel, and impact force is got over
Strong reaction is faster, but the material of D3O be because multiple impacts recovery can not be carried out, and protector average life span 2 years.POC company, Sweden is only
A kind of armor facing material of vertical exploitation, has high damping, is impacted to be hardened immediately and absorbs most impact energy, but
The material reaction speed is slower, and for integral material can not compound other materials be used in conjunction with, brick can be become temperature is too low
As it is hard, temperature it is excessively high and can such as sposh softness.The poron protective gear material of Rogers company, U.S. exploitation, is presented a kind of high
Density, fine and uniform cellular texture have the features such as high leakproofness, high resiliency, high fire-retardance, but absorb energy effect
It is not good enough, to reach same system's energy effect, protector seems thick and heavy.These above-mentioned material costs are higher, and large area enters to be had in the market
Certain difficulty.Moreover, these materials do not have the plastic function of low temperature, plastotype can not be carried out according to demands of individuals after human body dress
Adjustment.Also, these materials do not have high temperature reminiscence function, occur extremely influencing after Scrap marks appearance and subsequent make
With.
Many antagonism matches are very high to the personalized wearing requirement of protector, as used in sparring match and fencing match
Body large area protection and supporter, need to wear suitable protector.Commonly used on the market at present is cheap sponge back
The heart, this kind of protective articles influence movement effects.For example, mentioning a kind of can adjusting according to different statures for wearing in US0317899
Body protective tool, which is a kind of novel bundled fixed mode, rather than new diseases.Specifically: common protector
It can not be supplied to the fit wearing experience of different stature wearers, and will appear the danger for loosening sliding during the motion,
It causes that anti-fight protection can not be provided to wearer, the protector of sliding is also caused by the point of attack to other side force person and slides suddenly
The danger of caused physical contact part joint sprain.
In addition, effect of the shield tooth in protecting ware for sports is also particularly significant, collision is also extremely dangerous to the injury of tooth.Shield
Tooth can be divided into finished product shield tooth, and semi-finished product protect tooth and individual character protects tooth.It is mainly rubber, polyvinyl chloride, poly- second that finished product, which protects teeth material,
Sour ethylene rouge-polyethylene and ethylene copolymers.Finished product shield tooth is cheap, can not be modified according to demands of individuals, and wearing is uncomfortable, is easy to draw
Nausea is played, influences to move, gradually be eliminated.Personalization shield tooth is expensive and medical practitioner is needed to instruct, and material is main
For polyvinyl acetate-polyethylene and ethylene copolymers and EVA.Semi-finished product protect tooth effect and price between other between the two.Currently, mouth
Interior molding semi-finished product is divided into two classes, and one kind is the soft capsule shield tooth of hard shell, and one kind is thermoplastic high molecular material.The soft capsule shield of hard shell
Tooth is injection acrylic material and EVA in hard shell (polyvinyl chloride), serves as soft capsule, integral installation is on tooth.Thermoplastic is high
Molecular material is usually polyvinyl acetate-polyethylene and ethylene copolymers, then kept in the mouth occlusion molding by hot water heating.This two
The shield tooth of kind form can provide a degree of protective effect, but because plasticity is not high and the thermoplastic time is too short, cause
It wears and owes comfortable, and by heating repeatedly and saliva of buccal cavity is influenced, such life of product was short, no more than 2 years.
A kind of thermoplastics type's shield tooth is referred in US005339832A, there is the elastomer for absorbing energy to be embedded in facing, but its disadvantage
Still it is that plasticity is not strong.In addition, in protecting teeth of children field, it, can be accurate because Pediatric Oral Emergency development persistently changes shape
Plastotype and be product in short supply in the market with the shield tooth of memory function.
Summary of the invention
The purpose of the invention is to overcome the drawbacks described above of the prior art, a kind of polymer blend is provided, the polyester group
Preparation method and a kind of functional layer of conjunction object and preparation method thereof and their application.Polymer blend of the invention has
Good low-temp plastic and shape-memory properties.It therefore, can when polymer blend provided by the invention being used for protecting ware for sports
To carry out moulding according to the difference of application site, so that protector is more bonded body, more comfortable and easy to make；In addition, of the invention
Protecting ware for sports if there is abrasion or slight damage after, can again by heating softening moulding to protect again with low temperature
Tool restores original appearance.
To achieve the goals above, in a first aspect, the present invention provides a kind of polymer blend, with the total weight of each component
On the basis of, which contains following components:
(1) the polyester A, the polyester A of 50-98 weight % is containing shown in repetitive unit A shown in formula (I) and formula (II)
Repetitive unit B copolymer, and on the basis of the total mole number of repetitive unit A and repetitive unit B in the polyester A, institute
The content for stating repetitive unit A is 55-79 moles of %, and the content of preferably 60-77 moles of %, the repetitive unit B are rubbed for 21-45
You are %, preferably 23-40 moles of %,
Wherein, m1 is the integer of 2-4, and n1 is the integer of 2-4, and m1 and n1 are identical or different, and the polyester A's divides equally again
Son amount is 50,000-900,000；
(2) the polyester B, the polyester B of 1-49 weight % is contains repetitive unit C shown in formula (III) and formula (II) institute
The copolymer of the repetitive unit B shown, and on the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B,
The content of the repetitive unit C is 80-100 moles of %, and the content of preferably 85-95 moles of %, the repetitive unit B are 0-20
Mole %, preferably 5-15 moles of %,
Wherein, m2 is the integer of 2-4, and n2 is the integer of 2-4, and m2 and n2 are identical or different, and the polyester B's divides equally again
Son amount is 50,000-900,000；
(3) fiberfill of 1-49 weight %.
Second aspect, the present invention also provides the preparation method of above-mentioned polymer blend, which includes: will be above-mentioned
Polyester A, polyester B and fiberfill are blended, and obtained mixture is carried out extruding pelletization.
The third aspect, the present invention also provides a kind of functional layer, which contains above-mentioned polymer blend and/or by upper
State the polymer blend that preparation method obtains.
Fourth aspect, the present invention also provides a kind of preparation method of functional layer, which includes: above-mentioned polyester group
It closes object and/or is made by the polymer blend that above-mentioned preparation method obtains by molding.
5th aspect, the polymer blend obtained the present invention also provides above-mentioned polymer blend, by above-mentioned preparation method,
The application of above-mentioned functional layer, the functional layer obtained by above-mentioned preparation method in protecting ware for sports.
The present invention will be by that will have the polyester A, polyester B and fiberfill of specific structure according to specific proportion (50-98 weight
Measure the fiberfill of polyester B, the 1-49 weight % of polyester A, the 1-49 weight % of %) with the use of polymer blend is obtained, it should
(such as 80-100 DEG C) can sufficiently soften (hardness decline) under polymer blend hot conditions, and the polymer blend after softening can be with
The functional layer of arbitrary shape is made up of molding according to target site, allows to be preferably bonded with target site；Then exist
(such as -20-50 DEG C), hardness is significantly raised at lower temperature, to realize the purpose of moulding.Also, polyester provided by the invention
Composition also has good shape-memory properties, and deformation fixed rate is 90% or more, and deformation-recovery rate is up to 90% or more,
Largest deformation rate is up to 280% or more.In addition, the above-mentioned softening of polymer blend provided by the invention and moulding process are reversible
, when being made into protecting ware for sports, when protecting ware for sports occur wearing or slight damage after, can be again by heating
Moulding makes protector restore original appearance again for softening and low temperature.Therefore, protecting ware for sports made from functional layer provided by the present invention has
Good application prospect.
Detailed description of the invention
Fig. 1 is the cross-sectional view for the tooth protector finished product that the embodiment of the present invention 10 obtains, wherein 1 is oral cavity tooth
Set, 2 be oral cavity lower jaw facing；
Fig. 2 is the end perspective view for the tooth protector finished product that the embodiment of the present invention 10 obtains；
Fig. 3 is the end perspective view for the knee-pad finished product that the embodiment of the present invention 11 obtains, wherein 1 be knee-pad internal layer, 2
It is the outer layer of knee-pad for the middle layer of knee-pad, 3,4 be the convex portion on knee-pad superficies；
Fig. 4 is the isometric front view for the knee-pad finished product that the embodiment of the present invention 11 obtains, wherein 1 be knee-pad internal layer, 2
It is the outer layer of knee-pad for the middle layer of knee-pad, 3,4 be the convex portion on knee-pad superficies；
Fig. 5 is the isometric front view for the upper part of the body protector finished product that the embodiment of the present invention 12 obtains；
Fig. 6 is the sectional view for the upper part of the body protector finished product that the embodiment of the present invention 12 obtains, wherein 1 is upper part of the body protector
Internal layer, 2 be upper part of the body protector middle layer, 3 be upper part of the body protector outer layer；
Fig. 7 is the end perspective view for the helmet finished product that the embodiment of the present invention 13 obtains, wherein 1 be the helmet outer layer, 2
It is the internal layer of the helmet for the middle layer of the helmet, 3,4 be buckle.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of polymer blends, and on the basis of the total weight of each component, polyester combination
Object contains following components:
(1) the polyester A, the polyester A of 50-98 weight % is containing shown in repetitive unit A shown in formula (I) and formula (II)
Repetitive unit B copolymer, and on the basis of the total mole number of repetitive unit A and repetitive unit B in the polyester A, institute
The content for stating repetitive unit A is 55-79 moles of %, and the content of preferably 60-77 moles of %, the repetitive unit B are rubbed for 21-45
You are %, preferably 23-40 moles of %,
Wherein, m1 is the integer of 2-4；N1 be 2-4 integer, preferably 4；And m1 and n1 are identical or different；The polyester A
Weight average molecular weight be 50,000-900,000, preferably 100,000-500,000；
(2) the polyester B, the polyester B of 1-49 weight % is contains repetitive unit C shown in formula (III) and formula (II) institute
The copolymer of the repetitive unit B shown, and on the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B,
The content of the repetitive unit C is 80-100 moles of %, and the content of preferably 85-95 moles of %, the repetitive unit B are 0-20
Mole %, preferably 5-15 moles of %,
Wherein, m2 is the integer of 2-4；N2 be 2-4 integer, preferably 2；And m2 and n2 are identical or different；The polyester B
Weight average molecular weight be 50,000-900,000, preferably 100,000-500,000；Repetitive unit B's contains in the polyester A
Amount is greater than the content of the repetitive unit B in the polyester B；
(3) fiberfill of 1-49 weight %.
In the present invention, m1 and m2 can be identical or different, and n1 and n2 can be identical or different.But when m1 and m2 it is identical and
When n1 and n2 also identical, in the polyester A content of repetitive unit B in the polyester B repetitive unit B content not
Together.
In situations where it is preferred, the content of repetitive unit B is greater than the repetitive unit B in the polyester B in the polyester A
Content.
In the present invention, the weight average molecular weight of polymer is measured according to gel permeation chromatography (GPC).
In situations where it is preferred, the polymer blend contains the polyester B of polyester A, 5-30 weight % of 60-90 weight %
With the fiberfill of 5-30 weight %.
In the present invention, the polyester A and polyester B can be random copolymer, alternate copolymer, block copolymer
At least one of with graft copolymer, preferably random copolymer and/or block copolymer.The present invention to the polyester A and
There is no particular limitation in the source of the polyester B, can be obtained, can be commercially available by the means of this field routine,
Alternatively, can be prepared according to method disclosed in embodiment B13-B21 in CN100429256C.Specifically, the polyester A
Preparation method the following steps are included:
(1) in an inert atmosphere, monomer A and monomer B are reacted in the presence of the first catalyst；
(2) in an inert atmosphere, monomer C and monomer D are reacted in the presence of the first catalyst；
(3) by the reaction product obtained by step (1) and reaction product the depositing in the second catalyst obtained by step (2)
It is reacted under；
Wherein, the monomer A is butanediol；The monomer B is terephthalic acid (TPA) and/or its ester, preferably terephthaldehyde
At least one of acid, dimethyl terephthalate (DMT) and diethyl terephthalate；The dihydric alcohol that the monomer C is C2-C4 is (special
It is not saturated straight chain dihydric alcohol)；The monomer D is the binary acid (especially saturated straight chain binary acid) of C4-C6；Described first urges
Agent is at least one of butyl titanate, titanium dioxide, diethoxy titanium and zinc acetate, preferably butyl titanate；Institute
Stating the second catalyst is at least one of lanthanum acetylacetone, lanthanum trichloride, triple phenoxyl lanthanum and propionic acid lanthanum, preferably levulinic
Ketone lanthanum.
In the present invention, in step (1), the molar ratio of the monomer B and first catalyst is 1:0.0001-
0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
In the present invention, in step (2), the molar ratio of the monomer D and first catalyst is 1:0.0001-
0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
In situations where it is preferred, total dosage (the first catalyst in step (1) and step (2) of first catalyst
The sum of dosage) with the molar ratio of the dosage of second catalyst be 1:0.5-1.5, preferably 1:0.8-1.2.
In the present invention, the type of each reaction monomers can correspondingly be adjusted according to the composition and molecular weight of target product,
And control the content of each repetitive unit in the molecular weight and product of product respectively by adjusting inventory and feed ratio.
In the present invention, in step (1), the temperature of the reaction is preferably 160-220 DEG C；In the present invention, in step
Suddenly in (2), the temperature of the reaction is preferably 160-220 DEG C；In the present invention, in step (3), the temperature of the reaction is excellent
It is selected as 180-240 DEG C.
In the preferred embodiment of the present invention, when m1 is 4, the preparation method of the polyester A the following steps are included:
(S1) in an inert atmosphere, butanediol and monomer A ' are reacted in the presence of the first catalyst；
(S2) reaction product obtained by step (S1) and monomer B ' are reacted in the presence of the second catalyst；
Wherein, A ' is terephthalic acid (TPA) and/or its ester, preferably terephthalic acid (TPA), dimethyl terephthalate (DMT) and to benzene
At least one of dicarboxylate；Monomer B ' is the binary acid (especially saturated straight chain binary acid) of C4-C6；Described first
Catalyst and second catalyst are as described above, details are not described herein.
In the present invention, in step (S1), the molar ratio of the monomer A ' and first catalyst is 1:0.0001-
0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
In situations where it is preferred, the molar ratio of the dosage of first catalyst and the dosage of second catalyst is 1:
0.5-1.5, preferably 1:0.8-1.2.
In the present invention, the type of each reaction monomers can correspondingly be adjusted according to the composition and molecular weight of target product,
And control the content of each repetitive unit in the molecular weight and product of product respectively by adjusting inventory and feed ratio.
In the present invention, in step (S1), the temperature of the reaction is preferably 160-220 DEG C；In the present invention, in step
Suddenly in (S2), the temperature of the reaction is preferably 180-240 DEG C.
According to the present invention, the polyester B can be carried out according to the preparation method of above-mentioned polyester A, wherein can be according to target
The composition and molecular weight of product correspondingly adjust the type of each reaction monomers, and distinguish by adjusting inventory and feed ratio
The content of each repetitive unit in the molecular weight and product of product is controlled, to obtain polyester B.
According to the present invention, the fiberfill is carbon fiber, glass fibre, basalt fibre, aramid fiber and gathers to benzene
One of one or more of naphthalate fiber, preferably glass fibre, carbon fiber and basalt fibre or
It is several.Preferably, the length of the fiberfill is 0.1-10mm, preferably 0.5-2mm.
According to the present invention, the polymer blend can also contain auxiliary packing；Preferably, with the polymer blend
On the basis of total weight, the content of the auxiliary packing is 0.1-25 weight %, more preferably 1-20 weight %.
According to the present invention, the auxiliary packing, which has, accelerates composition melt solidification, regulation composition mechanical strength, adjusts
The effect of composition color and gloss etc. can be the conventional selection of this field, for example, the auxiliary packing can be carbon
One in Barbiturates inorganic filler, silicates inorganic filler, Sulfates inorganic filler, inanimate matter hollow microsphere and metal powder
Kind is several, preferably in carbonate inorganic filler, silicates inorganic filler, Sulfates inorganic filler and metal powder
At least one of one or more, more preferably dead plaster, calcium carbonate and copper powder.
Second aspect, the present invention also provides the preparation method of above-mentioned polymer blend, which includes: by polyester
A, polyester B and fiberfill are blended, and obtained mixture is carried out extruding pelletization.
In the preparation method of polymer blend of the invention, the composition of the polyester A, the composition of the polyester B, each group
The dosage divided is all as described above, and details are not described herein.
According to the present invention, described be blended in the presence of auxiliary packing carries out；Preferably, with the total of the polymer blend
On the basis of weight, the content of the auxiliary packing is 0.1-25 weight %, more preferably 1-20 weight %.
In the preparation method of polymer blend of the invention, the type of the auxiliary packing is as described above, herein no longer
It repeats.
In the present invention, inventor is surprised to find that in the course of the research: the polyester A, polyester B and fiberfill have
Therefore good compatibility can be added without compatilizer during blending.The compatilizer is commonly used in the art
For improving the substance of the compatibility of blended material, for example, can be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH
At least one of with PP-g-MAH.
According to the present invention, the process of the blending can carry out under stirring conditions.The present invention does not have the condition of stirring
There is special restriction, as long as raw material can be uniformly mixed, in situations where it is preferred, the rate of the stirring is 20-
150r/min, the time of the stirring are 5-15min.
According to the present invention, the extruding pelletization process can be implemented according to conventional extruding pelletization method, for example, described squeeze
Being granulated out can carry out in screw extruder.In situations where it is preferred, the temperature of the extruding pelletization is 120-240 DEG C, it is excellent
It is selected as 150-200 DEG C.
The third aspect, the present invention also provides a kind of functional layers, wherein the functional layer contain above-mentioned polymer blend and/
Or the polymer blend obtained by above-mentioned preparation method namely the functional layer are by above-mentioned polymer blend and/or by above-mentioned system
The polymer blend that Preparation Method obtains is made.
In the present invention, the functional layer has low-temp plastic and shape memory, specifically, in T1(80~100
DEG C) under the conditions of, the shore D type hardness tester value of the functional layer is 0-35；In T2Under the conditions of (- 20~50 DEG C), the functional layer
Shore D type hardness tester value is 40-80.That is, the functional layer can be in T1Soften under the conditions of (80~100 DEG C), at this time may be used
To carry out moulding to it by applying external force to obtain expected shape, after the completion of moulding, it is cooled to T2(- 20~50 DEG C) item
The hardness of part, the functional layer increases, and keeps shape.
Fourth aspect, the present invention also provides a kind of preparation method of functional layer, which includes: above-mentioned polyester group
It closes object and/or is made by the polymer blend that above-mentioned preparation method obtains by molding.
In the present invention, the functional layer of arbitrary shape and size can be made by forming according to the difference of application purpose.
According to the present invention, the molding mode can preferably be molded to squeeze out or being molded.Preferably, the injection molding
Temperature be 140-270 DEG C, preferably 170-185 DEG C.
5th aspect, the polymer blend obtained the present invention also provides above-mentioned polymer blend, by above-mentioned preparation method,
The application of above-mentioned functional layer, the functional layer obtained by above-mentioned preparation method in protecting ware for sports；Preferably, the protecting ware for sports is
One of tooth protector, extremities joint protector, body large area protector and head protector are a variety of.
In the present invention, term " tooth protector " refers to the protector to play a protective role during the motion to tooth.Institute
Stating tooth protector can preferably be made of the functional layer containing the functional layer.
In the present invention, the tooth protector has low-temp plastic and shape memory, specifically, in T1(80~100
DEG C) under the conditions of, the shore D type hardness tester value of the tooth protector is 0-35；In T2Under the conditions of (- 20~50 DEG C), the tooth shield
The shore D type hardness tester value of tool is 40-80.
The present invention also provides the preparation method of the tooth protector, which includes by function provided by the invention
Layer is successively softened, moulding and cooling are handled, and specifically, which includes: by the functional layer in T1(80~100
DEG C) under the conditions of soften, and moulding is carried out to it by applying external force (such as dental articulation), to obtain expected shape (such as tooth
Shape)；After the completion of moulding, it is cooled to T2The hardness of (- 20~50 DEG C) condition, the tooth protector increases, and keeps shape.
In the present invention, term " extremities joint protector " refer to during the motion, to extremities joint (for example, knee joint,
Elbow joint, shoulder joint, wrist joint etc.) protector that plays a protective role.The extremities joint protector contains the functional layer.
In situations where it is preferred, the extremities joint protector contains optional outer layer, middle layer and optional internal layer,
In, the middle layer is above-mentioned functional layer；The outer layer can be hard material, for example, can be metal material, rigid plastics
At least one of (not including polymer blend of the invention), ceramics and timber；The internal layer can be soft material, example
It such as, can be at least one of sponge, foam, soft silica gel and soft rubber.Also, the outer layer, middle layer are connected with internal layer
It connects；Preferably, the connection is realized by way of bonding (as used glue), screw thread or buckle.It is highly preferred that the outer layer,
Middle layer and internal layer are dismountable.
The present invention also provides the preparation method of the extremities joint protector, which includes: to provide the present invention
Functional layer successively softened, moulding and cooling processing, to obtain the middle layer of the extremities joint protector, specifically, should
Preparation method includes: by the functional layer in T1Soften under the conditions of (80~100 DEG C), and (be such as placed in pass by applying external force
The surface of section presses) moulding is carried out to it, to obtain expected shape (as in the shape being bonded with joint)；It is completed to moulding
Afterwards, it is cooled to T2The hardness of (- 20~50 DEG C) condition, the functional layer increases, and keeps shape, to obtain the extremities joint shield
The middle layer of tool.Optionally, the preparation method of the extremities joint protector further include: respectively in the outer surface of the middle layer
And/or inner surface connects outer layer and/or internal layer.Wherein, the outer layer and the internal layer are as described above, details are not described herein.
In the present invention, term " body large area protector " refers to during the motion to body main portions (for example, chest
Portion, back, waist, abdomen, thigh front, shank front etc.) protector that plays a protective role.The body large area protector contains
There is the functional layer.
In situations where it is preferred, the body large area protector contains outer layer, middle layer and optional internal layer, wherein institute
Stating middle layer is above-mentioned functional layer；The outer layer can be hard material, for example, (can not wrap for metal material, rigid plastics
Include polymer blend of the invention), ceramics and at least one of timber；The internal layer can be soft material, for example, can be with
For at least one of sponge, foam, soft silica gel and soft rubber.Also, the outer layer, middle layer are connected with internal layer；It is preferred that
Ground, the internal layer are connect by way of bonding with the middle layer；The middle layer and the outer layer by buckle, be bonded or
The fixed mode of bandage connects.It is highly preferred that the outer layer, middle layer and internal layer are dismountable.
The present invention also provides the preparation method of the body large area protector, which includes: to propose the present invention
The functional layer of confession is successively softened, moulding and cooling are handled, to obtain the middle layer of the body large area protector, specifically
Ground, the preparation method include: by the functional layer in T1Soften under the conditions of (80~100 DEG C), and by applying external force (as placed
Pressed in the surface of the physical feeling of application) moulding is carried out to it, to obtain expected shape (as in being bonded with physical feeling
Shape)；After the completion of moulding, it is cooled to T2The hardness of (- 20~50 DEG C) condition, the functional layer increases, and keeps shape, with
Outer layer is connected to the middle layer of the body large area protector, and in the outer surface of middle layer.Optionally, the body large area
The preparation method of protector further include: connect internal layer in the inner surface of the middle layer.Wherein, the outer layer and the internal layer are as above
Described, details are not described herein.
In the present invention, term " head protector " refers to the protector to play a protective role during the motion to head.It is excellent
Selection of land, the head protector are the helmet.
In the present invention, the head protector contains the functional layer.
In situations where it is preferred, the head protector contains optional outer layer, middle layer and optional internal layer, wherein institute
Stating middle layer is above-mentioned functional layer；The outer layer can be hard material, for example, (can not wrap for metal material, rigid plastics
Include polymer blend of the invention), ceramics and at least one of timber；The internal layer can be soft material, for example, can be with
For at least one of sponge, foam, soft silica gel and soft rubber.Also, the outer layer, middle layer are connected with internal layer；It is preferred that
Ground, the internal layer are connect by way of bonding with the middle layer；The middle layer and the outer layer by buckle, be bonded or
The fixed mode of bandage connects.It is highly preferred that the outer layer, middle layer and internal layer are dismountable.
The present invention also provides the preparation method of the head protector, which includes: by function provided by the invention
Ergosphere is successively softened, moulding and cooling are handled, to obtain the middle layer of the head protector, specifically, the preparation method
It include: by the functional layer in T1Soften under the conditions of (80~100 DEG C), and (be such as placed in the surface on head by applying external force
Pressing) moulding is carried out to it, to obtain expected shape (as in the shape being bonded with head)；After the completion of moulding, it is cooled to
T2The hardness of (- 20~50 DEG C) condition, the functional layer increases, and shape is kept, to obtain the middle layer of the head protector.It can
Selection of land, the preparation method of the head protector further include: connect internal layer in the inner surface of the middle layer and/or outer surface respectively
And/or outer layer.Wherein, the outer layer and the internal layer are as described above, details are not described herein.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, the weight average molecular weight of polymer uses gel permeation chromatography (GPC), with four
Hydrogen furans (THF) is solvent, in Waters-208 (band Waters 2410RI detector, 1.5mL/min flow velocity, 30 DEG C) instrument
Upper measurement, with the calibration of styrene standard specimen；
The composition of polymer blend passes through the determination that feeds intake of raw material；
In case of no particular description, the polyester that the present invention uses is according to embodiment B13- in CN100429256C
Method disclosed in B21 is voluntarily prepared, wherein can be according to the composition and molecular weight of target product, correspondingly adjustment reaction
The type of raw material, and each repetitive unit in the molecular weight and product of product is controlled respectively by adjusting inventory and feed ratio
Content.
Embodiment 1
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 5min) under stirring conditions, by 150g terephthalic acid (TPA) butanediol-
Adipic acid butanediol copolyester A (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and oneself two
On the basis of the total mole number of sour butanediol repetitive unit, the content of terephthalic acid (TPA) butanediol repetitive unit is 25 moles of %)
Grain, 20g terephthalic acid (TPA) butanediol-succinic acid butanediol copolyester B (weight average molecular weight 110,000, wherein to benzene two
On the basis of the total mole number of formic acid butanediol repetitive unit and succinic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol is repeated
The content of unit is 10 moles of %) particle, 20g glass fibre (Taishan glass fiber Ltd, model T536, similarly hereinafter) and
10g dead plaster (Tianjin Zhi Yuan chemical reagent Co., Ltd, analysis is pure, similarly hereinafter) is sufficiently mixed.The mixture that will be obtained
Extruding pelletization is carried out by double screw extruder, the revolving speed control of screw rod is 10rpm, torque 40N*m, in double screw extruder
The temperature of each section is followed successively by 180 DEG C, 190 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C from feed inlet to extrusion, is made poly-
Ester composition A1.
Embodiment 2
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 5min) under stirring conditions, by 171g terephthalic acid (TPA) butanediol-
Adipic acid butanediol copolyester A (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and oneself two
On the basis of the total mole number of sour butanediol repetitive unit, the content of terephthalic acid (TPA) butanediol repetitive unit is 40 moles of %)
Grain, 9.5g terephthalic acid (TPA) butanediol-succinic acid butanediol copolyester B (weight average molecular weight 110,000, wherein to benzene two
On the basis of the total mole number of formic acid butanediol repetitive unit and succinic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol is repeated
The content of unit is sufficiently mixed for 15 moles of %) particle, 9.5g glass fibre and 10g dead plaster.The mixture that will be obtained
Extruding pelletization is carried out by double screw extruder, the revolving speed control of screw rod is 10rpm, torque 40N*m, in double screw extruder
The temperature of each section is followed successively by 180 DEG C, 190 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C from feed inlet to extrusion, is made poly-
Ester composition A2.
Embodiment 3
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 5min) under stirring conditions, by 114g terephthalic acid (TPA) butanediol-
Adipic acid butanediol copolyester A (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and oneself two
On the basis of the total mole number of sour butanediol repetitive unit, the content of terephthalic acid (TPA) butanediol repetitive unit is 23 moles of %)
Grain, 57g terephthalic acid (TPA) butanediol-succinic acid butanediol copolyester B (weight average molecular weight 110,000, wherein to benzene two
On the basis of the total mole number of formic acid butanediol repetitive unit and succinic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol is repeated
The content of unit is sufficiently mixed for 5 moles of %) particle, 19g glass fibre and 10g dead plaster.Obtained mixture is led to
Cross double screw extruder and carry out extruding pelletization, the revolving speed control of screw rod is 10rpm, torque 40N*m, in double screw extruder from
The temperature of feed inlet to each section of extrusion is followed successively by 180 DEG C, 190 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, and polyester is made
Composition A3.
Embodiment 4
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
Under stirring conditions (rate of stirring be 30rpm, time 5min), by 95g terephthalic acid (TPA) butanediol-oneself
Diacid butanediol copolyester A (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and adipic acid
On the basis of the total mole number of butanediol repetitive unit, the content of terephthalic acid (TPA) butanediol repetitive unit is 45 moles of %) particle,
85.5g terephthalic acid (TPA) butanediol-succinic acid butanediol copolyester B (weight average molecular weight 110,000, wherein with terephthaldehyde
On the basis of the total mole number of sour butanediol repetitive unit and succinic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol repeats single
The content of member is sufficiently mixed for 20 moles of %) particle, 9.5g basalt fibre and 10g dead plaster.The mixture that will be obtained
Extruding pelletization is carried out by double screw extruder, the revolving speed control of screw rod is 10rpm, torque 40N*m, in double screw extruder
The temperature of each section is followed successively by 180 DEG C, 190 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C from feed inlet to extrusion, is made poly-
Ester composition A4.
Embodiment 5
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
Under stirring conditions (rate of stirring be 30rpm, time 5min), by 95g terephthalic acid (TPA) butanediol-oneself
Diacid butanediol copolyester A (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and adipic acid
On the basis of the total mole number of butanediol repetitive unit, the content of terephthalic acid (TPA) butanediol repetitive unit is 20 moles of %) particle,
9.5g polybutylene terephthalate (PBT) (being purchased from E.I.Du Pont Company, the trade mark is Crastin SC164 NC010) particle, 85.5g are profound
Military rock fiber and 10g dead plaster are sufficiently mixed.Obtained mixture is subjected to extruding pelletization, spiral shell by double screw extruder
The revolving speed control of bar is 10rpm, torque 40N*m, in double screw extruder from feed inlet to extrusion each section temperature according to
It is secondary be 180 DEG C, 190 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, be made polymer blend A5.
Embodiment 6
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
It carries out according to the method for embodiment 1, unlike, polyester A is total for terephthalic acid (TPA) butanediol-adipic acid butanediol
Polyester (weight average molecular weight 100,000, wherein repeated with terephthalic acid (TPA) butanediol repetitive unit and adipic acid butanediol single
On the basis of the total mole number of member, the content of terephthalic acid (TPA) butanediol repetitive unit is 25 moles of %)；Polyester B is terephthaldehyde
Sour butanediol-adipic acid butanediol copolyester (weight average molecular weight 110,000, wherein repeated with terephthalic acid (TPA) butanediol single
On the basis of the total mole number of member and adipic acid butanediol repetitive unit, the content of terephthalic acid (TPA) butanediol repetitive unit is rubbed for 10
You are %).Polymer blend A6 is made.
Embodiment 7
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
It carries out according to the method for embodiment 1, unlike, polyester A is total for terephthalic acid (TPA) butanediol-succinic acid ethylene glycol
Polyester (weight average molecular weight 200,000, wherein repeated with terephthalic acid (TPA) butanediol repetitive unit and succinic acid ethylene glycol single
On the basis of the total mole number of member, the content of terephthalic acid (TPA) butanediol repetitive unit is 25 moles of %)；Polyester B is terephthaldehyde
Sour butanediol-succinic acid glycol copolyester (weight average molecular weight 200,000, wherein repeated with terephthalic acid (TPA) butanediol single
On the basis of the total mole number of member and succinic acid ethylene glycol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is rubbed for 10
You are %).Polymer blend A7 is made.
Embodiment 8
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
It carries out according to the method for embodiment 1, unlike, polyester A is total for terephthalic acid (TPA) butanediol-adipic acid butanediol
Polyester (weight average molecular weight 500,000, wherein repeated with terephthalic acid (TPA) butanediol repetitive unit and adipic acid butanediol single
On the basis of the total mole number of member, the content of terephthalic acid (TPA) butanediol repetitive unit is 25 moles of %)；Polyester B is terephthaldehyde
Sour butanediol-succinic acid glycol copolyester (weight average molecular weight 500,000, wherein repeated with terephthalic acid (TPA) butanediol single
On the basis of the total mole number of member and succinic acid ethylene glycol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is rubbed for 10
You are %).Polymer blend A8 is made.
Embodiment 9
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
It carries out according to the method for embodiment 1, unlike, dead plaster is not added.Polymer blend A9 is made.
Comparative example 1
Carry out according to the method for embodiment 1, unlike, polyester A, 20g glass fibre that 170g embodiment 1 is used and
The mixing of 10g dead plaster, and it is added without the polyester B that embodiment 1 uses.Polymer blend D1 is made.
Comparative example 2
Carry out according to the method for embodiment 1, unlike, polyester B, 20g glass fibre that 170g embodiment 1 is used and
The mixing of 10g dead plaster, and it is added without the polyester A that embodiment 1 uses.Polymer blend D2 is made.
Comparative example 3
It carries out according to the method for embodiment 1, unlike, use the polybutylene terephthalate (PBT) (purchase of identical weight
From E.I.Du Pont Company, the trade mark is by Crastin SC164 NC010) replace polyester A used in embodiment 1.Polymer blend is made
D3。
Comparative example 4
It carries out according to the method for embodiment 1, unlike, use the polybutylene terephthalate (PBT) (purchase of identical weight
From E.I.Du Pont Company, the trade mark is by Crastin SC164 NC010) replace polyester B used in embodiment 1.Polymer blend is made
D4。
Comparative example 5
Carry out according to the method for embodiment 1, unlike, using identical weight poly butylene succinate (purchased from bar
Si Fu company, trade mark 1111HTA4, similarly hereinafter) replace polyester A used in embodiment 1 that polymer blend D5 is made.
Comparative example 6
It carries out according to the method for embodiment 1, unlike, it is added without glass fibre element.Polymer blend D6 is made.
Comparative example 7
It carries out according to the method for embodiment 1, unlike, the dosage of polyester A is 20g, and the dosage of polyester B is 150g.System
Obtain polymer blend D7.
Comparative example 8
It carries out according to the method for embodiment 1, unlike, by 190g polybutylene terephthalate (PBT) and the anhydrous sulphur of 10g
Sour calcium mixing.Polymer blend D8 is made.
Comparative example 9
It carries out according to the method for embodiment 1, unlike, by 190g poly butylene succinate and 10g dead plaster
Mixing.Polymer blend D9 is made.
Test case 1-18
1, hardness determination
After polymer blend made from embodiment 1-9 and comparative example 1-9 is melted respectively, under 170 DEG C, 1000MPa
5min is managed, 4mm thickness is pressed into, side length is the plate of 7cm.Hot sheet is taken out, with being placed in the frozen iron blocks of room temperature for a long time for plate
It is taken out after material quenching 1min and places 1h under room temperature (25 DEG C).Plate after placement is held into hardness using Drick shoreD
Meter measures, and measurement result is recorded after 15s.Then, which is heated to 90 DEG C in thermal station, again with same method
Measure shore D hardness.The results are shown in Table 1.
2, shape-memory properties detect
Polymer blend made from embodiment 1-9 and comparative example 1-9 is respectively prepared punching press batten, and by manufactured punching press
Batten carries out shape-memory properties test, and the results are shown in Table 1.The shape-memory properties of polymer blend use
Instron5965 tensilometer (band insulating box) measurement, specific as follows:
The initial length of polymer blend batten at room temperature is a；Insulating box is warming up to 80 DEG C, softens it sufficiently,
Length b is stretched under conditions of tensile speed is 50mm/min；It keeps external force to keep tensile elongation constant, cools down, it is solid to batten
Change, remove external force, the length of batten is c at this time；It batten is warming up to 80 DEG C again, sufficiently bounces back to batten, at this time batten
Length is d；
Deformation fixed rate (%)=(c-a)/(b-a) × 100%；
Deformation-recovery rate (%)=(c-d)/(c-a) × 100%；
Largest deformation rate (%)=bmax/ a × 100%, wherein bmaxAttainable maximum b before being damaged for batten.
Table 1
It can be seen from the result of the above table 1 compared with comparative example 1-9, the polymer blend of embodiment 1-9 is in higher temperatures
The hardness of (90 DEG C) is lower under degree, and the hardness of (25 DEG C) is significantly raised at a lower temperature, is easy to moulding.Also, embodiment
With higher this of the polymer blend of 1-9 illustrates polymer blend of the invention deformation fixed rate with higher (up to
90% or more), deformation-recovery rate (up to 90% or more) and largest deformation rate (up to 280% or more).The above result shows that this
The polymer blend that invention provides has good low-temp plastic and shape-memory properties.
Embodiment 10
The present embodiment is for illustrating protecting ware for sports provided by the invention and preparation method thereof.
The polymer blend A1 that embodiment 1 obtains is formed into tooth protector by way of injection molding, the temperature of injection molding is 170
DEG C, it injects in aluminium-making mould, (25 DEG C) of room temperature demouldings are at U-shaped mold.Obtained U-shaped mold is softened in 90 DEG C of hot water,
Then it is rapidly cooled to 0 DEG C, containing in entrance, forms contour after upper and lower dental articulation, tooth shield is obtained after polishing repeatedly
Has finished product.As illustrated in fig. 1 and 2.Fig. 1 is the cross-sectional view of tooth protector finished product, wherein 1 is oral cavity facing, and 2 be oral cavity
Lower jaw facing；Fig. 2 is the end perspective view of facing.
When tooth protector is worn or uses uncomfortable, tooth protector is softened in 90 DEG C of hot water again, then
Be rapidly cooled to 0 DEG C, containing in entrance, form contour after upper and lower dental articulation, retrieved after polishing repeatedly shape with
The tooth protector finished product that tooth is more bonded.
Embodiment 11
The present embodiment is for illustrating protecting ware for sports provided by the invention and preparation method thereof.
The polymer blend A1 that embodiment 1 obtains is formed into knee-pad middle layer by way of injection molding, the temperature of injection molding is
It 175 DEG C, injects in aluminium-making mould, obtains mold after room temperature (25 DEG C) stripping forming.By obtained mold in 90 DEG C of hot water
Softening, is then rapidly cooled to 0 DEG C, is placed in knee joint surface pressing, to form knee joint profile, obtains after polishing repeatedly
The middle layer of knee-pad.Then the inner surface of obtained knee-pad middle layer is connected by the internal layer of adhesive tape and cotton material, knee-pad
The outer surface of middle layer is connected by the outer layer of thread gluing and aluminum alloy material, can be taken out at any time.To by outer layer, middle layer and
Internal layer is assembled into knee-pad finished product together.As shown in Figures 3 and 4.Fig. 3 is the end perspective view of knee-pad finished product, wherein 1 is knee-pad
Internal layer, 2 be the middle layer of knee-pad, and 3 be the outer layer of knee-pad, and 4 be the convex portion on knee-pad superficies.Fig. 4 is knee-pad finished product
Isometric front view, wherein 1 be knee-pad internal layer, 2 be knee-pad middle layer, 3 be knee-pad outer layer, 4 be knee-pad superficies
On convex portion.
When knee-pad is worn or uses uncomfortable, knee-pad is softened in 90 DEG C of hot water again, it is then cooling rapidly
To 0 DEG C, it is placed in knee joint surface pressing, to form knee joint profile, obtains retrieving shape and knee after polishing repeatedly
The knee-pad middle layer that joint is more bonded.
Embodiment 12
The present embodiment is for illustrating protecting ware for sports provided by the invention and preparation method thereof.
The polymer blend A1 that embodiment 1 obtains is formed to the middle layer of upper part of the body protector by way of injection molding, is molded
Processing temperature be 180 DEG C, inject aluminium-making mould in, obtain mold after room temperature (25 DEG C) stripping forming.Obtained mold is existed
Soften in 90 DEG C of hot water, be then rapidly cooled to 0 DEG C, is pressed around the surface of the upper part of the body, to form upper part of the body profile, through anti-
The middle layer of upper part of the body protector is obtained after strike-on mill.Then the inner surface of the middle layer of obtained upper part of the body protector is passed through into adhesive tape
It is connect with the internal layer of spandex material, the outer surface of the middle layer of upper part of the body protector is connect by thread gluing with the outer layer of PBS material, can
To take out at any time.To which outer layer, middle layer and internal layer are assembled into upper part of the body protector finished product together.As illustrated in Figures 5 and 6.Fig. 5 is
The isometric front view of upper part of the body protector finished product.Fig. 6 is the sectional view of upper part of the body protector finished product, wherein 1 is the interior of upper part of the body protector
Layer, 2 be the middle layer of upper part of the body protector, and 3 be the outer layer of upper part of the body protector.
When upper part of the body protector is worn or uses uncomfortable, upper part of the body protector is softened in 90 DEG C of hot water again,
Then it is rapidly cooled to 0 DEG C, presses around the surface of the upper part of the body, to form upper part of the body profile, is obtained again after polishing repeatedly
Obtain the middle layer of shape with the upper part of the body protector being more bonded above the waist.
Embodiment 13
The present embodiment is for illustrating protecting ware for sports provided by the invention and preparation method thereof.
The polymer blend A1 that embodiment 1 obtains is formed into helmet middle layer, the processing temperature of injection molding by way of injection molding
Degree is 185 DEG C, injects in aluminium-making mould, obtains mold after room temperature (25 DEG C) stripping forming.Heat by obtained mold at 90 DEG C
Soften in water, be then rapidly cooled to 0 DEG C, is placed in head surface pressing, to form contouring head, is obtained after polishing repeatedly
The middle layer of the helmet.Then the inner surface of obtained helmet middle layer is connected by the internal layer of thread gluing and sponge material, knee-pad
The outer surface of middle layer is connected by the outer layer of thread gluing and aluminum alloy material.Outer layer, middle layer and internal layer are also fixed by snap,
It is assembled into helmet finished product together.As shown in Figure 7.Fig. 7 is the end perspective view of helmet finished product, wherein 1 is the outer layer of the helmet, and 2 are
The middle layer of the helmet, 3 be the internal layer of the helmet, and 4 be buckle.
When the helmet is worn or uses uncomfortable, the helmet is softened in 90 DEG C of hot water again, it is then cooling rapidly
To 0 DEG C, it is placed in head surface pressing, to form contouring head, obtains retrieving shape and head more after polishing repeatedly
The helmet middle layer of fitting.
It, can be with when polymer blend provided by the invention being used for protecting ware for sports it can be seen from above embodiments 10-13
Moulding is carried out according to the difference of application site, so that protector is more bonded body, more comfortable and easy to make；In addition, of the invention
After protecting ware for sports is if there is abrasion or slight damage, can again by heating softening moulding makes protector again with low temperature
Restore original appearance.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (13)
1. a kind of polymer blend, which is characterized in that on the basis of the total weight of each component, which contains with the following group
Point:
(1) the polyester A, the polyester A of 50-98 weight % is containing weight shown in repetitive unit A shown in formula (I) and formula (II)
The copolymer of multiple unit B, and on the basis of the total mole number of repetitive unit A and repetitive unit B in the polyester A, it is described heavy
The content of multiple unit A is 55-79 moles of %, and the content of preferably 60-77 moles of %, the repetitive unit B are rubbed for 21-45
You are %, preferably 23-40 moles of %,
Wherein, m1 is the integer of 2-4, and n1 is the integer of 2-4, and m1 and n1 are identical or different, the weight average molecular weight of the polyester A
For 50,000-900,000；
(2) the polyester B, the polyester B of 1-49 weight % is containing shown in repetitive unit C shown in formula (III) and formula (II)
The copolymer of repetitive unit B, and on the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B, it is described
The content of repetitive unit C is 80-100 moles of %, and the content of preferably 85-95 moles of %, the repetitive unit B are rubbed for 0-20
You are %, preferably 5-15 moles of %,
Wherein, m2 is the integer of 2-4, and n2 is the integer of 2-4, and m2 and n2 are identical or different, the weight average molecular weight of the polyester B
For 50,000-900,000；
(3) fiberfill of 1-49 weight %.
2. polymer blend according to claim 1, wherein the polymer blend contains the polyester of 60-90 weight %
A, the fiberfill of the polyester B and 5-30 weight % of 5-30 weight %.
3. polymer blend according to claim 1 or 2, wherein in formula (I), m1 be 2-4 integer, n1 be 4 it is whole
Number；
Preferably, the weight average molecular weight of the polyester A is 100,000-500,000.
4. polymer blend according to claim 1 or 2, wherein in formula (III), m2 is the integer of 2-4, n2 2；
Preferably, the weight average molecular weight of the polyester B is 100,000-500,000.
5. polymer blend according to claim 1 or 2, wherein the fiberfill is carbon fiber, glass fibre, profound
One or more of military rock fiber, aramid fiber and polyethylene terephthalate fiber, preferably glass fibre, carbon fiber
One or more of with basalt fibre；
Preferably, the length of the fiberfill is 0.1-10mm, preferably 0.5-2mm.
6. polymer blend described in any one of -5 according to claim 1, wherein the polymer blend also contains auxiliary
Filler；
Preferably, on the basis of the total weight of the polymer blend, the content of the auxiliary packing is 0.1-25 weight %, excellent
It is selected as 1-20 weight %；
It is filled out it is highly preferred that the auxiliary packing is carbonate inorganic filler, silicates inorganic filler, Sulfates are inorganic
One or more of material, inanimate matter hollow microsphere and metal powder, preferably carbonate inorganic filler, silicates are inorganic fills out
One or more of material, Sulfates inorganic filler and metal powder, more preferably in dead plaster, calcium carbonate and copper powder
It is at least one.
7. the preparation method of polymer blend described in a kind of any one of claim 1-6, which is characterized in that the preparation side
Method includes: polyester A, polyester B and fiberfill to be blended, and obtained mixture is carried out extruding pelletization.
8. preparation method according to claim 7, wherein described be blended in the presence of auxiliary packing carries out；
Preferably, on the basis of the total weight of the polymer blend, the content of the auxiliary packing is 0.1-25 weight %, excellent
It is selected as 1-20 weight %；
Preferably, the process of the blending is added without compatilizer.
9. preparation method according to claim 7 or 8, wherein the temperature of the extruding pelletization is 120-240 DEG C, preferably
It is 150-200 DEG C.
10. a kind of functional layer, which is characterized in that the functional layer contains the combination of polyester described in any one of claim 1-6
The polymer blend that object and/or the preparation method as described in any one of claim 7-9 obtain.
11. a kind of preparation method of functional layer, which is characterized in that the preparation method includes: any one of claim 1-6 institute
The polymer blend that the polymer blend and/or the preparation method as described in any one of claim 7-9 stated obtain passes through
Molding is made.
12. preparation method according to claim 11, wherein the molding mode is to squeeze out or be molded, and is preferably infused
Modeling；
Preferably, the temperature of the injection molding is 140-270 DEG C, preferably 170-185 DEG C.
13. polymer blend described in any one of claim 1-6, the system as described in any one of claim 7-9
Polymer blend that Preparation Method obtains, functional layer described in any one of claim 10, the preparation method as described in claim 11 or 12
Application of the obtained functional layer in protecting ware for sports；
Preferably, the protecting ware for sports is one in tooth protector, extremities joint protector, body large area protector and head protector
Kind is a variety of.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710703875.1A CN109401216B (en) | 2017-08-16 | 2017-08-16 | Polyester composition and functional layer, preparation method and application thereof |
| JP2019520899A JP2020502288A (en) | 2016-10-21 | 2017-10-20 | Polyester composition, its production method and its application |
| CA3040988A CA3040988A1 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| EP17862862.4A EP3530694A4 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| US16/343,711 US11466151B2 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| PCT/CN2017/107106 WO2018072746A1 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710703875.1A CN109401216B (en) | 2017-08-16 | 2017-08-16 | Polyester composition and functional layer, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109401216A true CN109401216A (en) | 2019-03-01 |
| CN109401216B CN109401216B (en) | 2022-07-12 |
Family
ID=65454679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710703875.1A Active CN109401216B (en) | 2016-10-21 | 2017-08-16 | Polyester composition and functional layer, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109401216B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117247609A (en) * | 2023-11-17 | 2023-12-19 | 河南恒发科技股份有限公司 | Low-damping high-performance rubber for new energy automobile suspension and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101495335A (en) * | 2005-03-08 | 2009-07-29 | 通用汽车环球科技运作公司 | Reversibly expandable energy absorbing assembly and methods for operating the same |
| CN102212966A (en) * | 2010-04-02 | 2011-10-12 | 财团法人塑胶工业技术发展中心 | Thermoplastic memory type three-dimensional mesh sheet material, high-air-permeability thermoplastic splint and safety protector |
| CN102810284A (en) * | 2011-06-03 | 2012-12-05 | 徐州市中通标准件有限公司 | Rotary display screen |
| CN102869723A (en) * | 2010-03-24 | 2013-01-09 | 巴斯夫欧洲公司 | Process for producing cling films |
| US20140004332A1 (en) * | 2012-06-27 | 2014-01-02 | Finetrack | Laminate of cloths, clothing, and bedding |
-
2017
- 2017-08-16 CN CN201710703875.1A patent/CN109401216B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101495335A (en) * | 2005-03-08 | 2009-07-29 | 通用汽车环球科技运作公司 | Reversibly expandable energy absorbing assembly and methods for operating the same |
| CN102869723A (en) * | 2010-03-24 | 2013-01-09 | 巴斯夫欧洲公司 | Process for producing cling films |
| CN102212966A (en) * | 2010-04-02 | 2011-10-12 | 财团法人塑胶工业技术发展中心 | Thermoplastic memory type three-dimensional mesh sheet material, high-air-permeability thermoplastic splint and safety protector |
| CN102810284A (en) * | 2011-06-03 | 2012-12-05 | 徐州市中通标准件有限公司 | Rotary display screen |
| US20140004332A1 (en) * | 2012-06-27 | 2014-01-02 | Finetrack | Laminate of cloths, clothing, and bedding |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117247609A (en) * | 2023-11-17 | 2023-12-19 | 河南恒发科技股份有限公司 | Low-damping high-performance rubber for new energy automobile suspension and preparation method thereof |
| CN117247609B (en) * | 2023-11-17 | 2024-02-23 | 河南恒发科技股份有限公司 | Low-damping high-performance rubber for new energy automobile suspension and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109401216B (en) | 2022-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103289179B (en) | A kind of High-elasticity sneaker air cushion sole and production method thereof | |
| EP1778786B1 (en) | Dental appliance and mouthguard | |
| CN1208002C (en) | Insert-molded helmet | |
| US6820623B2 (en) | Polyethylene dental appliance and mouthguard with tactifier resin | |
| JP4038625B2 (en) | Solid golf ball and method for producing solid golf ball | |
| US20070254256A1 (en) | Oral appliance | |
| CN1274258C (en) | Process for manufacturing protective helmets | |
| KR100368782B1 (en) | Flexible lightweight protective pad with energy absorbing inserts | |
| US20200237048A1 (en) | Composite materials, methods of making, methods of use, and articles incorporating the composite materials | |
| US3103217A (en) | Mouthpiece | |
| US20120121876A1 (en) | Elastomeric Composition | |
| JPH062174B2 (en) | Mouthpiece | |
| US5879244A (en) | Golf ball | |
| WO2011067005A1 (en) | Protective headgear | |
| CN109328202A (en) | The product made of hydrophilic thermoplastic's urethane composition | |
| US7867180B2 (en) | Immobilisation device | |
| US20040154625A1 (en) | Mouthguard and method of making the mouthguard | |
| CN109401216A (en) | Polymer blend and functional layer and its preparation method and application | |
| CN113929953A (en) | High-flexibility foaming sole material and preparation method of sole | |
| AU2021218473A1 (en) | Heat mouldable mouth guard | |
| US9827442B2 (en) | Thermoplastic sheet, a radiation mask of thermoplastic sheet and method for providing said sheet and said mask | |
| US11944507B2 (en) | Immobilisation device | |
| EP0903377A1 (en) | Polyurethane compositions | |
| CN103657014B (en) | A kind of ball for health and manufacture method thereof | |
| CN113975779A (en) | Flexible self-adaptation protective equipment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |