# US 11,028,334 B2 · Gradient copolymer, its production and application thereof

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- Number: US 11,028,334 B2
- Document ID: US11028334B2
- Status: Granted
- Kind: B2
- Application number: 16/313,869
- Filed: 2017-06-27
- Published: 2019-06-06
- Granted: 2021-06-08
- Earliest claimed: 2016-06-28
- Assignees: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Applicants: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Inventors: Yao Zhang; Qinghua Duan; Kecheng Wei; Yinong Liu; Hongwei Sun
- Web page: https://patentgrep.com/patent/US11028334B2

## CPC

- C10M 145/14: Acrylate; Methacrylate
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C08F 220/1811: {C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate}
- C10M 169/041: {the additives being macromolecular compounds only}
- C08F 220/1806: {C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate}
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08F 220/1818: {C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate}
- C10M 2203/003: used as base material
- C10M 2209/084: Acrylate; Methacrylate
- C10N 2030/02: Pour-point; Viscosity index
- C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS

## Abstract

A gradient copolymer comprises or consists of n polymer components. The n polymer components each independently represents an addition polymer of a monomer of the formula (I), and/or a mixture thereof, or the n polymer components each independently comprises or consists essential of one or more structural units represented by the formula (I-1), The symbol n represents an integer within the closed interval [5, ∞]. The average side chain carbon number of the i-th polymer component as determined according to the nuclear magnetic resonance method is expressed as Xi, with the symbol i representing an arbitrary integer from 1 to n, the relationship X1<X2< . . . <Xn−1<Xn holds.

## Claims

### Claim 1

A gradient copolymer comprising or consisting of a plurality of polymer components, wherein each of the plurality polymer components independently is an addition polymer of a monomer of formula (I), and/or a mixture of monomers of formula (I),
or
each of the plurality of polymer components independently comprises or consists essentially of one or more structural units of formula (I-1),
wherein a total number of the plurality of polymer components is n, and n is an integer within the closed interval [5, ∞], and in formula (I) or formula (I-1),
the group R1 is H or
the group R2 is H or a C1-4 linear or branched alkyl,
a is 0 or 1,
the group R′ is H or a group R3,
the group R3 is a C1-C30 linear or branched alkyl group, and
wherein an average number of carbon atoms in side chain of the i-th polymer component, as determined by nuclear magnetic resonance, is Xi, wherein i is an integer from 1 to n, and X1<X2< . . . <Xn−1<Xn,
wherein a weight percentage of the i-th polymer component relative to a total weight of the plurality of polymer components is Yi, and Y1<Y2< . . . <Yj> . . . >Yn−1>Yn,
wherein j is an integer within the closed interval [(n+1)/4, 3(n+1)/4], and
Y1+Y2+ . . . +Yi+ . . . +Yn−1+Yn=100%,
wherein Yi and Xi satisfy the following relationship,
Y
i
=
f
⁡
(
X
i
)
=
1
2
⁢
π
⁢
σ
⁢
e
-
(
X
i
-
μ
)
2
2
⁢
σ
2
,
(
IV
)
wherein μ is a value within the open interval (12.5, 14.2), and σ is a value within the open interval (0.5, 2).

### Claim 2 (depends on 1)

The gradient copolymer according to claim 1, wherein the gradient copolymer has an average number of carbon atoms in side chain, as determined by nuclear magnetic resonance, within a range from 5 to 20, or the number average molecular weight Mn of the plurality of polymer components or the gradient copolymer is each independently from 10,000 to 1,000,000, or the molecular weight distribution Mw/Mn of the plurality of polymer components or the gradient copolymer is each independently from 1.8 to 3.5.

### Claim 3 (depends on 1)

The gradient copolymer according to claim 1, wherein the monomer of formula (I) is one or more selected from the group consisting of C6 linear alkyl (meth)acrylates, C8 linear alkyl (meth)acrylates, C10 linear alkyl (meth)acrylates, C12 linear alkyl (meth)acrylates, C14 linear alkyl (meth)acrylates, C16 linear alkyl (meth)acrylates, C18 linear alkyl (meth)acrylates, and C20 linear alkyl (meth)acrylates.

### Claim 4 (depends on 1)

The gradient copolymer according to claim 1, wherein a proportion (by mole) of the one or more structural units of formula (I-1), in which the group R3 is a C10-C18 linear or branched alkyl group, relative to the total amount of the structural units constituting each of the plurality of polymer components, is from 40% to 95%.

### Claim 5 (depends on 1)

The gradient copolymer according to claim 1, wherein said X1 is a value within the closed interval [6.5, 12.5], or said Xn is a value within the closed interval [13.8, 19.5].

### Claim 6 (depends on 1)

The gradient copolymer according to claim 1, wherein said Yj is within a range from 20% to 75%, or said Y1 or Yn is within a range from 0.01% to 20%.

### Claim 7 (depends on 1)

A method for producing the gradient copolymer according to claim 1, comprising:
adding at least two monomers to a polymerization system, and conducting an addition copolymerization of the at least two monomers, wherein the at least two monomers each independently is a compound of formula (I),
and
in formula (I),
the group R1 is H or
the group R2 is H or a C1-4 linear or branched alkyl,
a is 0 or 1,
the group R′ is H or a group R3,
the group R3 is a C1-C30 linear or branched alkyl group, and
wherein the starting time of adding the at least two monomers to the polymerization system is t0, and the termination time is tm, the addition time of the at least two monomers is t and t=tm−t0, and wherein the addition time is divided into m segments, m is an integer within the closed interval [5, ∞],
wherein, during the addition of the at least two monomers, a ratio between the at least two monomers added to the polymerization system at any moment of time tx, the symbol x representing an integer from 0 to m, varies such that the average number of carbon atoms in side chain Xx of a resulting mixture composed of the at least two monomers as determined by nuclear magnetic resonance satisfies the following relationship,
X0<X1< . . . <Xm−1<Xm.

### Claim 8 (depends on 7)

The production method according to claim 7, wherein, at the termination time tm of the addition, a sum of the cumulative amounts of the at least two monomers added to the polymerization system through the addition time t is G, and a sum of the amounts of the at least two monomers added to the polymerization system at any moment of time tx during the addition of monomers is Gx, and
G0/G<G1/G< . . . <Gj/G> . . . >Gm−1/G>Gm/G,
wherein j is an integer within the closed interval [m/4, 3m/4].

### Claim 9 (depends on 7)

The production method according to claim 7, wherein the at least two monomers are two or more selected from the group consisting of a C6 linear alkyl (meth)acrylate, a C8 linear alkyl (meth)acrylate, a C10 linear alkyl (meth)acrylate, a C12 linear alkyl (meth)acrylate, a C14 linear alkyl (meth)acrylate, a C16 linear alkyl (meth)acrylate, and a C18 linear alkyl (meth)acrylate; or
two or more selected from the group consisting of a C8 linear alkyl (meth)acrylate, a C10 linear alkyl (meth)acrylate, a C12 linear alkyl (meth)acrylate, a C14 linear alkyl (meth)acrylate, a C16 linear alkyl (meth)acrylate, a C18 linear alkyl (meth)acrylate, and a C20 linear alkyl (meth)acrylate.

### Claim 10 (depends on 7)

The production method according to claim 7, wherein the proportion (by mole) of the compound of formula (I), in which the group R3 is a C10-C18 linear or branched alkyl group, relative to the total amount of the monomers is within a range from 40% to 95%.

### Claim 11 (depends on 7)

The production method according to claim 7, wherein said X0 is a value within the closed interval [6.5, 12.5], or said Xm is a value within the closed interval [13.8, 19.5].

### Claim 12 (depends on 8)

The production method according to claim 8, wherein the ratio Gj/G is within a range from 20% to 75%, or the ratio G0/G or the ratio Gm/G is within a range from 0.01% to 20%.

### Claim 13 (depends on 1)

A method for producing the gradient copolymer according to claim 1, comprising the step of mixing a plurality of polymer components, wherein each of the plurality of polymer components is an addition polymer of a monomer of formula (I),
and/or a mixture of monomers of formula (I), or
each of the plurality of polymer components independently comprises or consists essentially of one or more structural units of formula (I-1),
wherein the number of the plurality of polymer components is p and p is an integer from 5 to 10000, and
in formula (I) or formula (I-1),
the group R1 is H or
the group R2 is H or a C1-4 linear or branched alkyl,
a is 0 or 1,
the group R′ is H or a group R3,
the group R3 is a C1-C30 linear or branched alkyl group,
where the average number of carbon atoms in side chain of the i-th polymer component, as determined by nuclear magnetic resonance, is Xi, wherein i is an integer from 1 to p, and X1<X2< . . . <Xp−1<Xp.

### Claim 14 (depends on 13)

The production method according to claim 13, where the weight percentage of the i-th polymer component relative to the total weight of the plurality of polymer components is Yi, wherein i is an integer from 1 to p, and Y1<Y2< . . . <Yj> . . . >Yp−1>Yp,
wherein j is an integer within the closed interval [(p+1)/4, 3(p+1)/4], and Y1+Y2+ . . . +Yj+ . . . +Yp−1+Yp=100%.

### Claim 15 (depends on 13)

The production method according to claim 13, wherein the proportion (by mole) of the one or more structural units of formula (I-1), in which the group R3 is a C10-C18 linear or branched alkyl group, relative to the total amount of the structural units constituting each of the plurality of polymer components is within a range from 40% to 95%.

### Claim 16 (depends on 13)

The production method according to claim 13, wherein said X1 is a value within the closed interval [6.5, 12.5], or said Xp is a value within the closed interval [13.8, 19.5].

### Claim 17 (depends on 14)

The production method according to claim 14, wherein said Yj is within a range from 20% to 75%.

### Claim 18 (depends on 1)

A lubricating oil composition comprising the gradient copolymer according to claim 1, and a lubricating base oil, wherein, on the basis of the gradient copolymer, the content by weight of the gradient copolymer in the lubricating base oil is within a range from 0.01 wt % to 2 wt %.

### Claim 19 (depends on 1)

A method of lowering a pour point of a lubricating oil, comprising the step of adding the gradient copolymer of claim 1 into the lubricating oil.

### Claim 20 (depends on 7)

The method according to claim 7, wherein the at least two monomers are at least two selected from the group consisting of a C10 linear alkyl (meth)acrylate, a C12 linear alkyl (meth)acrylate, a C14 linear alkyl (meth)acrylate, a C16 linear alkyl (meth)acrylate, a C18 linear alkyl (meth)acrylate and a C20 linear alkyl (meth)acrylate; or
are at least two selected from the group consisting of a C8 linear alkyl (meth)acrylate, a C14 linear alkyl (meth)acrylate, a C16 linear alkyl (meth)acrylate, a C18 linear alkyl (meth)acrylate, and a C20 linear alkyl (meth)acrylate.